905R80100
00471
QUALITY ASSURANCE PROGRAM
GUIDELINES AND SPECIFICATIONS
CRITERIA AND PROCEDURES
REGION V
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TABLE OF CONTENTS
PAGE
1. Identification of Office of Laboratory Submitting QA Plan 1
2. Quality Assurance Policy Statement, Region V 3
3. Objectives and Milestones 5
4. Quality Assurance Management 7
4.1 Introduction. 7
4.2 Quality Assurance Management Plan 8
4.2.1 Assignment of Responsibilities 9
4.2.2 Flow of Information 11
4.2.3 Identification of QA - Related Committees or Meetings 12
4.2.4 Description of Needs 13
5. Personnel 14
6. Facilities, Equipment and Services 17
7. Review of Program Plans, Project Plans or Study Plans 18
8. Data C ol 1 ecti on 20
8.1 Sampling Plan 20
8.2 Sampling Methodology 21
8.3 Analytical Methodology 32
8.3.1 Maintenance of Up-To-Date File of Measurement Methods...37
8.3.2 Alternate Test Procedure Program 40
8.3.2.1 Elements of an Application for a National Pollutant
Discharge Elimination System (NPDES) of Section 106
Alternate Test Procedure 41
8.3.2.2 Elements of an Application for a Safe Drinking
Water Act (SDWA) Alternate Test Procedure 48
8.3.2.3 Processing of Case-By-Case Alternate Test Procedure
in Region V 51
8.3.2.4 Procedures for Equivalent Test Procedure Under the
Clean Air Act 53
8.4 Instrument at i on 53
8.5 Calibration and Standards 54
8.6 Preventive Maintenance and Inspections 55
8.7 Qua! i ty C ontrol Procedures 57
8.7.1 Intra-Laboratory Quality Control Procedures... 57
8.7.1.2 Intra-Field Quality Control Procedures 63
8.7.1.3 Additional Intra-Laboratory Quality Control
Procedures for Specific Groups of Parameters 65
8.7.2 Inter-Laboratory Quality Control Procedures 71
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TABLE OF CONTENTS (CONTINUED)
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8.7.2.1 Management of the Accuracy and Performance
Audit Programs 72
8.7.2.2 Management of the On-Site System Evaluation of Total |
In-House, Federal, State and Local Agency,
Contractor, Grantee Monitoring Program 76 _
9. Data Processing 78
9.1 Data Handling Transmission and Storage 78
9.2 Data Validation and Verification 86
9.3 Data Reduction (Including Software QC Considerations) 92 |
10. Corrective Actions 93
10.1 QA Management 95
10.2 QC Management 95
11. Data Quality Assessment 97
11.1 Accuracy Assessment 98 I
11.2 Precision Assessment 98
11.3 Completeness Assessment 98
11.4 Represent!'veness Assessment 98 |
11.5 Overall Data Quality Assessment 99
12. Data Quality Reports (QC and QA) 99 I
13. Chain of Custody 100
14. Specific Guidance 106 |
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APPENDIX 1
APPENDIX 2
APPENDIX 3
APPENDIX 4
APPENDIX 5
APPENDIX 6
APPENDIX 7
APPENDIX 8
APPENDIX 9
APPENDIX 10
APPENDIX 11
APPENDIX 12
APPENDIX 13
APPENDIX 14
APPENDIX 15
APPENDICES
Quality Assurance Office FY 80 Work Plan
Relationship of the Quality Assurance Function to
Other Regional Program Functions
The Organizational Structure of Region V
State of Wisconsin Department of Natural Resources,
Bureau of Air Management, Air Monitoring Section,
Quality Assurance Manual - Procurement
Sample Collection Containers, Preservatives and Holding
Times for Sample Collection in the 106, 208, 404(b)(l)
and the Great Lakes National Monitoring Programs
EPA Official Analytical Methodology - Priority Pollutant
Measurements
EPA Official Analytical Methodology - Hazardous Waste
Measurements
Sample Collection, Preservation, and Holding Times -
Ambient Air Samples
EPA Official Analytical Methodology - Water Quality
Measurements
EPA Official Analytical Methodology - Radiation Methods
EPA Official Analytical Methodology - Ambient Air
Measurements
EPA Official Analytical Methodology - Source Air
Measurements
EPA Offical Analytical Methodology - Public Water
Supply Methods
Sample Collection Containers, Preservatives, and Holding
Times for Samples Collected in the 1412 Monitoring Program
Approved Alternative Analytical Methods - Nationwide Use.
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APPENDIX 16
APPENDIX 17
APPENDIX 18
APPENDIX 19
GLOSSARY
APPENDICES (Continued)
Performance Tests for the Evaluation of Computerized
Gas Chromatography/Mass Spectrometry Equipment and
Laboratories
Life Cycle of an On-Site System Evaluation
Elements for a Section 106, 208, 404(b)(l) and Great
Lakes Program Monitoring Quality Assurance Program
Summary of Guidelines for Station Siting and Probe
Placement
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1. IDENTIFICATION OF OFFICE OR LABORATORY SUBMITTING QA PLAN
Document Title:
Units Full Name
and Address:
Individual
Responsible:
Individual
Responsible
for QA:
Plan Prepared By:
Submission Date:
Calendar Year
Covered:
Quality Assurance Program
Guidelines and Specifications
Criteria and Procedures
Region V
Ref. NO.:
EPA-905/4-80-001
U.S. Environmental Protection Agency
230 South Dearborn Street
Chicago, Illinois 60604
John McGuire
Regional Administrator
Region V
U.S. Environmental Protection Agency
230 South Dearborn Street
Chicago, Illinois 60604
(FTS)353-2000
William H. Sanders III
Director
Surveillance and Analysis Division
U.S. Environmental Protection Agency
Region V
536 South Clark Street
Chicago, Illinois 60605
(FTS)353-3808
James H. Adams, Jr.
Chief
Quality Assurance Office
Surveillance and Analysis Division
U.S. Environmental Protection Agency
Region V
536 South Clark Street
Chicago, Illinois 60605
(FTS)353-9604
January 15, 1980
Interim document will be used pending finalization
of Agency Quality Assurance Plan.
Summary of environmental monitoring or measurement activities performed
by Region V:
Quality assurance activities have been planned for 1980 in Air
Quality Monitoring, Air Enforcement, Dredge and Fill, Ambient Water
Quality Monitoring, Water Quality Enforcement, Public Water Supply
Management and Great Lakes Monitoring. There are also special
studies, contracts and other activities that require evaluation
for quality assurance.
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INTRODUCTION
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Environmental Protection Agency (EPA) Policy, enunciated in memoranda
of May 30 and June 14, 1979, requires participation in a centrally-managed |
Quality Assurance Program by all EPA Regional Offices, Program Offices,
EPA Laboratories, and the States. This includes those monitoring and «
measurement efforts mandated or supported by EPA through regulations,
grants, contracts, or other formalized agreements. The Quality Assurance
Programs for the States in Region V will be cooperatively developed with
them and implemented through the Regional Office.
The Office of Research and Development (ORD) has been given the responsi-
bility for developing, coordinating, and directing the implementation M
of the Agency Quality Assurance Program. In addition, an Agency Quality I
Assurance Advisory Committee, chaired by ORD and with representatives
from the Program Offices, Regional Offices, Staff Offices, and the
States, has been established to coordinate this effort.
At this point, the distinction between two concepts -- quality assurance
and quality control -- becomes relevant. "Quality Assurance" is defined
here as an organization's total program for assuring the reliability
of data it produces. A QA Plan is a document presenting the policies,
objectives, management structure, and general procedures which comprise
this total program. "Quality Control" refers to the detailed and
specific procedures used to ensure the quality of data produced by a
particular measurement activity. For example, a QA Plan for laboratory
instruments would state that calibration needs to be addressed as an
element of data collection activities. It would not, however, give |
instructions about how to do this calibration; these instructions
represent quality control.
As an initial step in implementing this policy, Quality Assurance
Plans (Programs) must be prepared by all EPA-supported or -required
environmental monitoring and measurement activities per the specifications
of EPA's guidance document MQA 001-79. |
EPA policy is quite clear that the Agency Quality Assurance Program _
encompasses all environmentally related measurement activities undertaken
by the Regional Offices, Program Offices, State Program Offices, and
Laboratories; supported by these divisions through contracts, grants,
or other formalized agreements; or required by them through regulations.
A very broad definition of "environmentally related measurement I
activities" has been adopted. It includes all field and laboratory
investigations which generate data. The measurement of chemical,
physical or biological parameters in the environment; health and
ecological effects studies; clinical and epidemiologic investigations;
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studies involving laboratory measurements or simulated environmental
events are covered under this definition and all such activities must
be covered by a Quality Assurance Plan.
This document describes the Quality Assurance Program for Region V,
U.S. EPA, that will produce a numerical estimate of the reliability of
all data values reported or used by the Region.
2. QUALITY ASSURANCE POLICY STATEMENT. REGION V
It is the policy of EPA, Region V that there shall be sufficient
quality assurance activities conducted within the Region to assure
the collection of data which meet the requirements of the Environmental
laws and regulations that require implementation by EPA in Region V.
The Regional Administrator has the overall responsibility for
implemenation of the Agency's quality assurance program for valid
data quality. The Director of the Surveillance and Analysis
Division (S&A), through the Chief of the Quality Assurance Office
(CQAO), assures that quality assurance objectives are met for each
monitoring project conducted within Region V. This responsibility
also includes external monitoring activities of States, local
agencies, contractors and others covered by the Agency quality
assurance plan.
The immediate objective of the Quality Assurance Office is to insure
that the quality of data collected, reported or used by the Agency
is properly documented and that the data are sufficiently accurate
and precise to meet the Agency's quality assurance objectives.
The following activities shall be carried out in accordance with
Agency mandates specified in document MQA 001-79, and existing
Agency regulations.
The Quality Assurance Program will consist of:
1. An adequately trained staff for implementation of the
Region's quality assurance program as approved by ORD.
2. Equipment procurement and maintenance shall meet
specifications required by regulations, approved
methodology, or appropriate EPA guidelines and shall
be approved by the CQAO. These requirements shall
appply to all Region V monitoring activities and to
State and local agencies when Federal funds are
expended.
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3. Analytical methods and procedures for all monitoring p
programs shall conform to EPA approved methodology
when applicable, and shall include quality control H
measures. All methods and procedures shall be
documented "cookbook fashion" and reviewed and approved
or revised as required by Agency regulations and
guidelines. Their revisions and updates shall be
by the appropriate Agency mechanism, based on |
recommendations from the CQAO.
4. The Regional Administrator, based upon recommendations I
from the CQAO, through the Director, Surveillance and m
Analysis Division, shall approve State and local agency
Quality Assurance policies and programs.
5. Region V and State and local laboratory and field
monitoring facilities shall perform system and
performance audits. These facilities shall participate
in inter!aboratory audits managed by the AQAC and
coordinated with EMSL-RTP, EMSL-Cincinnati and EMSL-Las Vegas-.
6. Data processing shall be documented, reviewed and
revised as required by the Region's Quality Assurance
Program and approved by the Office of Research and
Development. Quality control measures must assure gj
accurate data from analysis by Region V, State and
local agencies. Data shall be validated according
to criteria which shall follow EPA guidelines and I
regulations.
7. Directors of the several divisions in Region V have
responsibilities for the quality of data collected |
and used in the performance of tasks required. These
responsibilities are corroborated under this policy.
The CQAO will coordinate the implementation criteria
for validation of required data. "
8. Standard operating procedures for air monitoring
activities in Region V, State and local agencies for
site selection, audits, evaluations, maintenance and
enforcement shall be developed, documented and M
reviewed per the requirements of 40 CFR Part 58.
9. The CQAO shall report continuously on all Quality
Assurance programs to program managers.
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CONCURRErCE
. .
Ctfief, Quality Assurance "Office,
Surveillance & Analysis Division,
Region V
Date
COfCURRENCE
APPROVED
Director, Surveillance & Analysis
Di v>s~NDn, Jtegi on V
/
1 Date
w
egional Administrator
Regjion V
Date
3. OBJECTIVES AND MILESTONES
The primary goal of the Region V, quality assurance program is to
define and improve the reliability (accuracy and precision) of
data generated and used by the Region, per Headquarters' mandate
and Agency regulations. There must be a mechanism for so doing.
In order to measure or estimate changes in data quality, the
quality must be expressed in measurable (numerical) terms. There-
fore, the first priority in the Region V quality assurance program
is to establish and implement a trethod to define and quantitate
the program product - data qualify. This includes data from Regional
programs, State and local agencies, grants and contracts. Each
- program that collects data is to be quality assured by a comprehensive
evaluation and review process such that all of the activities that
influence the quality of data are performed by appropriated trained
staff, by methods acceptable to EPA on instruments that are approved
and maintained and each data collection activity has a documented
quality controlled program.
MILESTONE 1: Interim Region V Quality Assurance Program will be
developed by the QAO by January 15, 1980. This program will be
amended and updated to meet the Agency's final QA requirements for
1981 within 90 days after final guidance from Headquarters becomes
available.
MILESTONE 2: All Regional Program Offices that are engaged in a
field sample collection activity shall prepare a field sampling
and quality control manual which documents their methods of sample
collection, preservation, field custody, field instrument calibrations
and field quality control protocol, plus any other requirements
specified in Section 8 of this document, by April 15, 1980. These
documents will be submitted to the QAO for review and recommendations
to the Regional Administrator for approval by Sampling programs
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Included are air, hazardous waste, toxic substances, priority pollutants, |
public water supply, ambient surface and ground water, NPDES and
Great Lakes. Programs are to be updated per the requirements of
new Agency regulations or guidelines.
MILESTONE 3: All Laboratories in the Surveillance and Analysis
Division engaged in analysis of samples shall document their
methodology and quality assurance/control program per the specifications I
in Section 8 of this document, by April 15, 1980 and submit such
documentation to the QAO for review and recommendations to the Regional
Administrator for approval. Programs are to be updated per the I
requirements of new Agency regulations or guidelines. m
MILESTONE 4: All State's Water Agency(s) shall document their field
and laboratory methodology and quality assurance/conrol program per |
the specifications in Section 8 of this document according to the
dates specified in each State's 106 grant condition by the Regional
Administrator. These documents are to be forwarded to the respective I
State Coordinator for processing through the media manager and the
S&A Division to the QAO for review and recommendations to the
Regional Administrator for approval as required by Agency regulations.
MILESTONE 5: All State and Local Air Agency(s) shall document
their field and laboratory methodology and quality assurance/control
program per the specifications in Section 8 of this document by
January 1, 1980 to the respective State Coordinator for processing m
through the respective media managers and the S&A Division to the
QAO for review and recommendations to the Regional Administrator
for approval. I
OBJECTIVE: Manage the quality assurance functions in Region V that H
impacts all factors that influence data quality in the Region's I
FY 80 program plan. The factors to be considered are personnel,
equipment, procurement, methodology, legal requirements, organizational
responsibilities where QA policies must be carried out and other
factors. The implementation of an effective program will insure I
objectivity, self review and documentation so that cost effectiveness
in the program is assured. Objectives have been identified for each
program decision unit for FY 80, which are depicted in Appendix 1. I
MILESTONE 1: Key action steps(milestones) have been finalized
with due dates for objectives listed under each decision unit for
FY 80, which is also depicted in Appendix 1. |
OBJECTIVE: To establish an interaction at all levels of management
such that QA principles ara implemented.
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MILESTONE 1: These interractions are in place and are illustrated
in Appendix 2.
OBJECTIVE: To have QA resources assigned to QAO in proportion to
need, rather than programs controlling resources by which priorities
in those programs preclude resource commitment to QA as the program
planning process specifies and the National QA program mandates.
MILESTONE 1: During the planning process for FY 81, the QAO will
identify all activities that have QA requirements. Assess resource
needs for enumeration of those QA activities. Formulate FY 81 QAO
Zero Based Budget activities with QA committments. This resource
assessment will encompass implementation of the Region's FY 81 QA
plan (program) as approved by ORD.
4. QUALITY ASSURANCE MANAGEMENT
4.1 Introduction
The current quality assurance program that is functional in
Region V during FY 80 evolved from the program planning process
and is carried out under restrictions which are placed on QA
by resource commitments and priorities that are established
by programs which provide those resources. The organizational
structure of Region V which relates to data collectors and
decision making based on results of collected data is shown
in Appendix 3.
A description of the Organization for present QA related
activities follows:
WATER DIVISION: Has responsibilities in the public water supply,
ambient surface and ground water and wastewater programs.
The administration of these programs through grants results
in data collection by State and local personnel. Resources
(Appendix 1) for quality assurance are provided through Decision
Units B-224 (Ambient Water Quality Monitoring) and C-215
(Public Water Supply Management).
AIR AND HAZARDOUS MATERIALS DIVISION: Has responsibilities
for air programs, hazard waste management, pesticide and toxic
substances. Programs are managed through grants and contracts.
Technical and field support is provided by the S&A Division
through activities of the District Offices, Technical Support
Branch and the Central Regional Laboratory. Resources for
quality assurance are provided through Decision Units A-235
(Air Quality Monitoring), A-305 (Air Enforcement), and A-305
(Air Enforcement Unleaded Gas Inspections).
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ENFORCEMENT DIVISION: Has responsibilities for enforcement I
action in the various programs for compliance with Agency
regulations. QA of data collection is important to the
validation of data so that it can be defended in legal processes.
Resources are provided for QA in the A-305 Decision Unit for
PSD monitoring. However, QA support is provided in the B-303
Decision Unit by the QAO without resources being provided by I
the Enforcement Division.
PLANNING AND MANAGEMENT DIVISION: Maintains data processing
facilities and handle data for special studies and STORET. |
Although the data unit processes data collected by other
organizations, it produces final'reports from data which _
may require summary or collation for final data reporting. I
Thus, it is in the overall process, a data producer. QA
has no resource support for this division. QA programs have
not been employed.
S&A DIVISION: Is responsible for surveillance and analysis in
the various water, air, waste and toxic substance programs. _
Technical support, monitoring and project studies are carried
out for the program offices. Resources for QA in these various
functions of the S&A Division are those described under the
other divisions. S&A Division branches support QA programs by
auditing, sample collection, and special studies. |
GREAT LAKES NATIONAL PROGRAM OFFICE: The Great Lakes are monitored -
under this program through grants and contracts for sample I
collection and shore laboratory analysis, as well as, the
operation of the ship for open waters and shipboard analysis
by contract. Technical and field support is also provided by
the S&A Division through activities of the District Offices,
Technical Support Branch and the Central Regional Laboratory.
Resources for QA is provided under Decision Unit B-241 (Great
Lakes). |
4.2 Quality Assurance Management Plan
In this context the implementation of a quality assurance I
program is deemed as a management endeavor which attempts to
interface all activities which impact data quality, be they
management, technology, statistics, monitoring or maintenance.
In order to assure the data quality, each of the numerous |
activities must respond to the basic needs from which data
becomes possible.
When one realizes that the simplest item may become a
critical item in data collection, it then becomes apparent
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how the many disciplines work in concert. The QA program
will not presume that certain activities occur. It will require
that documentations and controls be implemented and evaluated
for effectiveness on a prescribed frequency basis. These
evaluations describe deficiencies and corrective actions
requi red.
In the formulation of the QA plan for Region V the mandates
for carrying out QA are documented in the Quality Assurance
Policy (Section 2). In this policy, management has designated
responsibilities and the individual who bear those responsibil-
ities. The organizational structure into which the QA management
interacts is established by this policy (Appendix 2). Adminis-
tratively, the QAO may be shown in a different relationship.
4.2.1 Assignment of Responsibilities
The Quality Assurance Office located in the Surveillance and
Analysis Division has the responsibility of managing Region
V's quality assurance program.
The Quality Assurance Office (QAO) establishes policies
and guidelines for regional, state and local quality assurance
programs, and conducts independent audits. Quality control,
i.e., quality and documentation of data used by regional/state/
local personnel, is the responsibility of the data generator.
The mission of the QAO is to ensure through implementation of the
quality assurance program so that the quality of data collected,
reported or used by the Region is properly documented and that
the data are sufficiently accurate and precise to meet Regional
program needs. The Quality Assurance Office is responsible
for developing and implementing procedures (programs) to
insure the reliability of laboratory data supporting the
air, pesticides, solid waste and toxic substances programs
in the Air and Hazardous Materials Division, the public
drinking water, ambient surface and ground water, and industrial
and domestic wastewater programs in the Water Division;
enforcement actions in the Enforcement Division; the Inter-
national Joint Commission, the harbor dredging programs in
the Great Lakes National Program Office, and all other programs
generating environmental data for the Region.
QAO conducts annual on-site system evaluations. The
evaluations are of the quality assurance and quality control
programs of State laboratories and monitoring facilities that
carry out testing under the Clean Air Act, Clean Water Act,
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Resource Conservation and Recovery Act, Safe Drinking Water |
Act and the Toxic Substances Control Act. In some instances
local agencies are evaluated where state responsibility has
been delegated. QAO identifies deficiencies, recommends I
corrective action and monitors effectiveness of action taken.
The QAO reviews state program plans for compliance with Agency I
requirements for quality assurance and analytical methodology
used in laboratories and field operations. The QAO coordinates
quality assurance programs with Agency regulations, program
guidance and media strategy.
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The on-going management of the laboratory certification program,
pursuant to the Safe Drinking Water Act, is the responsibility
nf the OAfL This function also involves continued aualitv
of the QAO. This function also involves continued quality
assurance activities for certified laboratories; an overview
of state certification programs for certification of local
laboratories and the performance of State certification officers.
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The Quality Assurance Office manages an inter!aboratory audit _
program which provides an extensive reference and quality I
control sample program for cooperating Federal, Canadian, *
State and local agencies, and private laboratories in Region V.
Approximately 123 laboratories participate in this program. |
Up to 316 different parameters are analyzed on a regular
basis. The audits cover air, public water supply, ambient
water (large lakes included), wastewater, dredging (sediments) I
and toxic pollutant laboratory analytical activity. These
audits are extremely important for the determination of accuracy
of laboratory performance. Results are evaluated and recommendations
made for corrective actions for any deficiencies identified. I
The management of the alternate test procedure program for
compliance with the Safe Drinking Water Act, National Pollution I
Discharge Elimination System and other regulations, is the
responsibility of the QAO. This function includes technical
interepretation of the regulations relating to test procedures, I
coordination of applications, evaluation of applicants' technical
data for equivalency and recommendations for approval or
disapproval.
The QAO participates in quality assurance activities for
the International Joint Commission Water Quality Board's _
monitoring activities on the Great Lakes. This function includes I
critical reviews of technical reports, maintenance of approved
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analytical methods and methods under consideration for approval,
official interpretations of method equivalency for regulatory
actions and defends regional data generated by approved procedures.
The QAO is responsible for providing, as requested, review
and technical assistance concerning Agency analytical methodology
and quality assurance requirements for State and local environmental
agencies, NPOES dischargers, public water supplies, source
emissions, etc. The QAO interprets National and Regional EPA
policies in the areas of analytical methodology and quality
assurance.
The QAO is responsible for the management of the quality ,
assurance requirements for all Region V external projects
involving collection and analytical measurements, which includes,
but is not limited to, grants, contracts, cooperative agreements,
and interagency agreements. The QAO's primary function is to
insure that all analytical measurements conducted with Regional
funding results in usable data of known quality that is acceptable
for Region V's purposes. The air responsibility includes
maintenance ind primary calibration of field and laboratory
equipment re ative to air pollutants measurements, and step-by-step
demonstrations of all facet* of instrument maintenance, calibration
and operation.
4.2.2. Flow of Information
The QAO is assigned activities under decision units which
require evaluation of data producing systems. The S&A Director
establishes priorities and delegates resources to the various
tasks. These tasks are identified in the annual work plan.
The QAO identifies goals to accomplish the objectives of the
decision units per the specification from Headquarters program
guidance from the Regional media programs, (for example, evaluation
of QA programs for air monitoring in State Agencies). The QAO,
through the S&A Director, establishes contact with State Agenciei and
arranges for information about the State's program and an on-site
visit. Information obtained prior to an on-site visit is evaluated,
the on-site evaluation is performed and an evaluation report is
prepared. The evaluation is reported through the S&A Director
to the State, to the Regional Air Program Office and the State
Coordinators. Corrective action, deficiencies and recommendations
are reported. States report corrective action taken or give
reasons for not taking action to the QAO. Should the
corrective action be of such a nature that an on-site
visit is required to verify that the action was appropriate.
<\ visit is requested through the S3A Director: The on-site visit
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is reported in a similar manner to the original evaluation report |
stating the findings and indicating satisfactory or non-satisfactory
results and recommending future action as required. _
When problems exist in which no correction is made and a dispute
results, the findings with recommendations are reported to the
Program Office and to the State Coordinators for resolution.
If a State program is involved and the program office is unable |
to resolve the problem and an impasse is reached, the
Regional Administrator makes a final determination of the _
unresolved issue based on recommendations from the QAO and
program office. Basically two major types of reports are
generated by the QAO. They are accuracy and performance audits
and on-site system evaluation reports. The content of these
reports are outlined in Section 8.7.2 and Subsection 8.7.2.1 |
of this document.
Based on the frequency identified in the QAO program plan
(Section 12), the QAO will write interpretative reports to *
management. These reports will be made on a regular basis
and will identify areas of work that could be improved and
areas that are being performed properly or in an exceptional |
manner. These reports will be based on information obtained
during on-site evaluations, from reviews of performance sample _
analyses and from evaluations of routine quality control I
audit data.
4.2.3 Identification of QA - Related Committees or Meetings
Quality assurance requirements/information are transmitted |
within Region V through meetings called by the QAO with affected
Regional media personnel. These are on an as needed basis. m
Documentation is also provided by way of memoranda.
Quality assurance requirements/information are transmitted
to State and local agency laboratory directors and quality
assurance coordinators by written communcations from the Quality |
Quality Assurance Office on a as needed basis. QA information
is also disseminated through the audit and on-site evaluation of _
Regional, State and local agency monitoring activities during
the frequencies specified in the QAO's FY 80 program plan
(Appendix 1).
The QAO will conduct two workshops in FY 80 for.public water |
supply analysts. The workshops will be for standardizing metal
analyses and for upgrading organic analyses for public water
supply laboratories. The Central Regional Laboratory will I
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provide technical support to the QAO in this endeavor by making
their laboratory facilities available and having their personnel
participate in the workshops.
The QAO has identified State and local air program agencies
that are in need of technical assistance in the area of quality
assurance and laboratory capability. Through a contract that
EMSL-RTP has in place, the QAO will work with the contractor
to upgrade those agencies that are in need of technical assistance.
This activity will commence the 2nd quarter of FY 80.
A workshop for audits of air monitoring sites will be conducted
by QAO and RTP at Region V in March 1980 for Region, State
and local agency personnel engaged in auditing air monitoring
sites.
The Quality Assurance Office participates in the Agency's
regularly scheduled semi-annual QA coordinator's meeting where
the Agency's QC concerns are addressed. The QAO participates in
national short term QA tasks as requested by the National Program.
The Chief, QAO has been appointed to the Data Quality Work
Group, Surveillance Sub-Committee, International Joint Commission,
Water Quality Board. The Data Quality Work Group has the
responsibility of assuring the quality of data from participating
laboratories engaged in the Surveillance Sub-Committee's Great
Lakes Surveillance Plan. All IX QA activities are implemented
through the Data Quality Work Group. The Work Group meets
monthly.
4.2.4 Description of Needs
The following resources are required to accomplish the QA
objectives and milestones identified in the interim QA program
for Region V.
A. Staff - Twelve man years of effort is required to fully
implement the Quality Assurance Program for Region V.
Sixty-six (66) percent of staff is in place. Present
staff consist of the Office Chief, 1 secretary, 2 professional
chemists, 1 professional microbiologist, 1 professional
physical scientist, 1 journeyman organic chemist and
1 journeyman electronics technician. Professional organic
chemistry support is provided to the QAO on an as needed
basis from the CRL (this support will continue for the
"hands on" experience). The type of additional staff
required (34%) is 1 professional organic chemist, 1
statistician (or chemist with a good statistical background)
and 2 journeyman inorganic chemists.
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I
Monetary - The QAO needs approximately $120,000 for
contracts. These contracts are to be used to develop
software EDP capability for measurement methods and
statistical data evaluation for minimum turn around Jj
time. Data quality problems could be identified much
faster and larger volumes of data can be evaluated.
Time - If all resources identified in Section 4.2.4 are I
granted the QAO, the program described in this document
could be fully implemented in 90 days after receipt of
resources.
Training Seminars - The QAO is providing workshops for
standardizing metal analyses and upgrading organic _
analyses performance for Region V and State laboratory
personnel during the second quarter of FY 80-. A workshop
for audits of air monitoring sites will also be provided
Region V, State and local agency personnel. Travel funds
will be required to get personnel to these workshops I
when their agency can not afford to send them.
Approximately $2,000 is required for this travel.
Key personnel of the Quality Assurance Office must have sufficient
administrative and technical stature to be considered a peer to I
the Managers of monitoring activities within the Region and to the
Managers of Region V State and local laboratories. This staff
must have a professional knowledge/training and understanding of I
chemical/microbiological principles, concepts, practices, established I
methodology and measurement (instruments) systems. The individual
must have at least two years of bench experience in his/her speciality,
particularly in an environmental laboratory. The individual must
have experience in developing and implementing intralaboratory
quality control programs. Regional QAO personnel must have knowledge
of Federal laws, Agency regulations and guidelines pertaining to I
quality assurance and analytical procedures related to the Agency's I
regulatory monitoring programs. The individual must be experienced
in meeting and dealing with Regional, State and local government
officials and other Federal Agencies.
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Analytical operations in the laboratory can be graded according
to the degree of complexity. Some analyses require no sample
treatment, and the measurement can be performed in minutes on a
simple instrument. Other determinations require extensive sample
preparation prior to complex instrumental examination. Consequently,
work assignments in the laboratory should be clearly defined.
Each analyst should be completely trained and should fully understand
all the assignments of his job before being given new responsibilities.
In this regard, all analysts, subprofessional or professional, should
be thoroughly instructed in basic laboratory operations, according
to the extent of professional maturity. Some of the basic operations
that will be reviewed with laboratory personnel during the on-site
evaluation follow.
a. SAMPLE LOGGING: Routine procedure for recording of samples
entering the laboratory and assigning primary responsibility
should be emphsized. The information that is required and the
routing of the samples to the analyst is then established. The
stability, preservation, and storage of samples prior to
analyses are then discussed.
b. SAMPLE HANDLING: The analyst should understand thoroughly at
which points in his procedures the sample is to be settled,
agiated, pipetted, etc., before he removes it from the original
contai ner.
c. MEASURING: The analysts, especially new employees and sub-
professionals, should be instructed in the use of volumetric
glassware. The correct use of pipettes and graduates should be
emphasized.
d. WEIGHING: Because alsmost every measuring operation in the
analytical laboratory is ultimately related to a weighing
operation, the proper use of the analytical balance should be
strongly emphasized. Maintenance of the balance, including
periodic standardization, should be repeatedly emphasized to
all personnel.
e. GLASSWARE: All glassware should be washed and rinsed according
to the requirements of the analysis to be performed. Not only
must the personnel assigned to these tasks be instructed, but
also all lab personnel should know the routine for washing and
special requirements for particular uses of glassware. In
addition, the precision tools of the the laboratory such as
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pi pets, burets, graduates, and tubes should be inspected before
use for cleanliness, broken delivery tips, and clarity of
marking. Defective glassware should be discarded or segregated.
INSTRUMENTATION: Operation and maintenance of analytical
instrumentation is of primary consideration in the production
of valid data. All instruments must meet the requirements I
specified in Agency regulations, be properly calibrated,
quality-control checks documented, and standard curves verified
on a routine basis. References on instrumental quality control
are presented in Section 8.4 and 8.5 of this document.
I
DATA HANDLING AND REPORTING: As with sample logging, the routine
procedure for recording results of analyses and pertinent
observations, including quality control checks, should be
emphasized. Analytical data should be permanently recorded in
meaningful, exact terms and reported in a form that permits
future interpretation and unlimited use. Details are discussed |
in Section 9 of this document.
QUALITY CONTROL: The need to continuously assess precision and I
recovery values of methodology is a prime responsibility of the
analyst. Self-evaluation through the analyses of QC samples,
replicates and recovery of spikes from samples representative
of the daily workload provides confidence and documentation
of the quality of the reported data.
SAFETY: Laboratory safety should be discussed on a continuing I
basis with all employees, but it should be emphasized when an
employee is assigned to perform new duties.
IMPROVEMENT: In summary, quality control begins with basic
laboratory techniques. Individual operator error and laboratory
error can be minimized if approved techniques are consistently
practiced. To insure the continued use of good technique, lab- g
oratory supervisors should periodically review the basic techniques
and point out areas of needed improvement with each analyst. _
Continuing improvement of technical competence by all laboratory
personnel is, of course, the final responsibility of the
laboratory supervisor. In a well-organized laboratory, however,
a big-brother attitude of higher ranking to lower grade personnel |
should be encouraged; each person should be eager to share
experience, tricks of the trade, special skills, and special _
knowledge with subordinates. Obviously, efficiency and results
will improve.
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k. SKILLS: The cost of data production in the analytical lab-
oratory is based largely upon two factors: the pay scale of the
analyst, and the number of data units produced per unit of time.
However, because of the large variety of factors involved,
estimates of the number of measurements that can be made per
unit of time are difficult. If the analyst is pushed to produce
data at a rate beyond his capabilities, unreliable results may
be produced. On the other hand, the analyst should be under
some compulsion to produce a minimum number of measurements per
unit of time, lest the cost of data production become prohibitive.
In table 5-1, estimates are given for the number of determinations
that an analyst should be expected to perform on a routine basis.
The degree of skill required for reliable performance is also
indicated.
The time limits presented in the table are based on use of
approved methodology. A tacit assumption has been made that
multiple analytical units are available for measurements requiring
special equipment, as for cyanides, phenols, ammonia, nitrogen,
and COD. For some of the simple instrumental or simple volumetric
measurements, it is assumed that other operations such as
filtration, dilution, or duplicate readings are required; in such
cases the number of measurements performed per day may appear
to be fewer than one would normally anticipate.
6. F/CILITIES. EQUIPMENT. AND SERVICES
The QA program makes Facilities, Equipment and Services a major
component of the program. The recognition is made that no data
can be collected without the appropriate equipment that is functional.
To assure the operation of that equipment all facilities, equipment
and services must work as a composite in a smooth orderly manner.
The items that are necessary are:
A. Laboratory facilties, building, utilities, equipment and maintenance.
B. Field facilities, housing for equipment, transportation require-
ments, utilities, supplies, communications and maintenance.
C. Analtytical equipment, required methods, operation and calibration
manuals, maintenance, parts and supplies.
D. Procurement procedures, that require purchase of the required
equipment with warrantees, demonstrated satisfactory performance
prior to payment, service arrangements, availability of spare
parts, evaluation of equipment from information of prior users,
costs evaluation and comparisons against competitive equipment.
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TABLE 5-1
SKILL-TIME RATING OF STANDARD ANALYTICAL OPERATIONS
Measurement
Simple Instrumental:
-pH
~" Conductivity
'"'Turbidity
Color
~~Dissolved Oxygen (Probe)
Fluoride (Probe)
Simple Volumetric:
Alkalinity (Potentiometric)
Acidity (Potentiometric)
Chloride
Hardness
Dissolved Oxygen (Winkler)
Simple Gravimetric:
Solids, Suspended
Solids, Dissolved
Solids, Total
Solids, Volatile
Simple Colori metric:
Nitrate N (Manual)
Nitrate N (Manual)
Sulfate (Turbidimetric)
Silica
Arsenic
Complex, Volumetric, or Colorimetric:
BOD
COD
TKN
Ammoni a
Phosphorus, Total
Phenol (Distillation Included)
Oil and Grease
Fluoride (Distillation Included)
Cyanide
Special Instrumental:
TOC
Metals (by AA), No Preliminary Treatment
Metals (by AA) , With Preliminary Treatment
Organics (by GC), Pesticides, Without Cleanup
Organics (by GC), Pesticides, With Cleanup
iSki 11 -required rating numbers are defined as foil
1 - aide who is a semiskilled subprofessional
comparable to GS-3 through GS-5.
Skill Required
(Rating No.)1
1
1
1
1
1,2
1,2
1
1
1
1
1,2
1,2
1,2
1,2
1,2
2
2
2
2
2,3
2,3
2,3
2,3
2,3
2,3
2,3
2,3
2,3
2,3
2,3
2,3
2,3
3,4
3,4
ows:
with minimum background
2 - aide with special training or professional with minimum training
in general laboratory techniques and some
GS-5 through GS-7.
3 - experienced analyst capable of following
knowledge of chemistry,
complex procedures with
Number
Per Day
100-125
100-125
75-100
60-75
100-125
100-125
50-75
50-75
100-125
100-125
75-100
20-25
20-25
25-30
25-30
75-100
40-50
70-80
70-80
20-30
215-20
25-30
25-30
25-30
50-60
20-30
15-20
25-30
8-10
75-100
150
60-80
3-5
2-4
or training.
with background
comparable to
good background
in analytical techniques, professional, comparable to GS-9 through GS-12.
4 - experienced analyst specialized in highly
oo + A comparable to GS-11 through GS-13.
ZRate depends on type of samples.
complex procedures, professional,
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E. Preventive Maintenance policies and procedures. |
F. Service and Repair procedures. _
G. Audit and Evaluation requirements.
H. Safety.
A protocol for procurement testing is described in Appendix 4 I
which establish guidelines for equipment that are based on
EPA guidelines, good laboratory practices and pertinent information
from industries and governmental agencies where similar concerns I
are part of the art of good management and quality assurance.
As with other operations, the effectiveness of facilities are
determined by independent evaluations.
7. REVIEW OF PROGRAM PLANS. PROJECT PLANS. OR STUDY PLANS
As a statement of policy, the QA program requires a review of all |
program project and study plans for Region V, including the S&A
Division study plans. It is essential that these plans are evaluated
from the beginning so that the appropriate measurement method is
selected that will produce the data the user needs. Many, if not
all, projects require data that lead to decisions that have an
economic impact as well as technologic impact. The prevention of
loss in monies, resources and time weighs heavily upon the plans |
that lead to program or project development. If those plans incorporate
unapproved, and inappropriate methodology which in turn produce _
data that are not pertinent to the program or project or do not
have acceptable precision, accuracy, representiveness or completeness,
then the efforts are lost, lead to wrong decisions, or cause equivocation.
Since the review of plans has not been customary in the past, it |
will be necessary to develop programs that accomplish this preliminary
review process. The various divisions and program units and QA
must work together to initiate this process as a Standard Operating I
Procedure. The details that need to be accomplished are:
A. Directives to Program, Project or study offices requiring QA
review of scope and plans at the earliest data of the planning
process.
B. Request of QA review requirements must be in writing. This
request should give some estimate of the magnitude of study.
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C. QAO, immediately upon initiation of the review process, would:
1. determine expertise required
2. technology
D. Having established plans for review, the QA review would proceed
and results would be reported. The evaluation would declare
feasibility with respect to provisions that assure the appropriate
methodology, precision, accuracy, representativeness and completeness.
Should factors be inappropriate or deficient, corrective measures
would be stated to the project officer.
The Agency's protocol for evaluation of QA plans in extramural
projects and contracts will be used as soon as the document is
available.
QAO will investigate the needs for developing guidelines which
would be used to evaluate statistical, modeling, and other aspects
of environmental studies. The location of expertise and at times
technology for unusual projects will require national concern. Thus
these.needs will be formulated as they become appropriate.
A review of programs, projects or study plans would determine what
QA plans are to be incorporated in those plans. The various activities
and items that must be identified are:
o Staffing (personnel in numbers, qua!ifiication and training).
o Methods (EPA approved methods must be used where required).
Procedures must be documented and made available for review
prior to use.
o Quality control measures must be described in detail.
This would explain the frequency of duplicate, spike or
performance samples. Control measures used in sample
collection, with frequency of duplicate sampling prescribed.
Audits by inter!aboratory, peer group, systems audits and
performance audit must be described as to frequency and source
of audit. Control limits must be determined and the
required measures that must be taken when out of control
limits have been exceeded should be described.
o Sample collection and preservation should be described
in detail. The calibrations of analytic methods and
equipment must be according to the requirements of the
approved methods. Standards used for calibrations must
be of the highest purity and referenced to MBS standards
whenever possible. Calibration procedures and tracability
must be documented.
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The QA plans must appear early in the planning process because
without these QAO will not have suitable information to move forward
in the evaluation process. .
Suitable procedural information for developing QA plans based on *
the items discussed above are available in the references cited
in Section 14 of this document.
8. DATA COLLECTION
Data quality changes occuring during data collection can come I
from six major activities: a) formulating sound objectives for the
sampling program, b) collecting representative samples, c) maintaining
sample integrity through proper sample handling and preservation,
d) adhering to appropriate sample identification and, where needed,
chain of custody procedures, e) practicing quality assurance pro-
cedures in the sample transportation, storage, and preparation
processes, and f) using proper analytical techniques complete with |
appropriate quality control activities to generate the actual data.
8.1 Sampling Plan I
The objectives of the sampling program affect all the
other aspects of the sampling program. Sampling program objectives
are determined by the following activities: (a) planning (areawide
or basin), (b) permits, (c) compliance, (d) enforcement, (e) design, |
(f) process control, and (g) research and development. The types
of sampling programs to be employed, depending on suitability to g
program objectives, include reconnaissance surveys, point- source
characterization, intensive surveys; fixed- station- network monitoring,
ground-water monitoring, ambient air monitoring and stationary
source emission monitoring, and special surveys involving chemical, I
biological, microbiological, and radiological monitoring.
Factors that must be considered in meeting the objectives of m
the sampling program are the extent of the manpower resources, the
complexity of the parameters of interest, the duration of the survey,
the number of samples, the frequency of sampling, the type of
samples (grab or composite), and the method of sample collection I
(manual or automatic). I
The media activity will identify the need for a sampling activity
in Region V. A person with lead responsibility in the media activity
is also identified to coordinate the project for the media activity.
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The identified need is transmitted to the S&A Division. The
Technical Support Branch coordinates the formulation of
objectives and goals for the sampling activity with the
Central Regional Laboratory and the appropriate District Office.
Once goals have been formulated to accomplish objectives
(including the six major activities listed under 8 above),
the proposal is then reviewed by the QAO to insure that all
quality assurance requirements for producing valid data have
been included. If any QA changes are needed, the QAO will
specify the changes needed. Once the QA changes are made
(if need be), the QAO will concur. The S&A Division Director
will transmit the study proposal to the Director of the
requesting media program for review and see if the defined objectives
and goals meets the program needs. If not, revision will be made
(NOTE - QA is not to be compromised). Once the Director of the media
program concurs in the proposal, the appropriate S&A Division
Office/Branch or other Divisions will initiate the proposal.
8.2 Sampling Methodology
The objective of sampling is to obtain a representative
portion of the total environment under investigation. The
sampling plan shall contain, as a minimum, the following
factors for concurrence by the QAO (Item 8.1 above) in formulation
of the sampling plan.
A. Water and Wastewater
o Site Selection
The location of the sampling site is critical in obtaining
representative data. Preferably, water sampling sites for
point sources of pollution from municipal and industrial
effluents are located at points of highly turbulent flow
to insure good mixing; however, inaccessibility, lack of
site security, or power unavailability may preclude use
of the best sites, but these impediments should not be
used as reasons for collecting samples at unacceptable
locations. Loctions of sampling sites for streams,
lakes, impoundments, estuaries, and coastal areas vary,
but in general occur in the following bodies: (a) in
water bodies for sensitive uses (swimming and drinking water
supply), (b) in major impoundments or reservoirs near the mouths
of major tributaries and in the rivers entering and leaving the
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impoundments, (c) in water bodies polluted by man's activities, |
(d) in rivers upstream and downstream from tributaries, and
(e) where hydrological conditions change significantly. _
o Sample Type
The basic types of water and wastewater methods are grab
sampling and composite sampling. Composite sampling may be I
conducted manually or automatically. The six methods
for forming composite samples, all of which depend on
either a continuous or periodic sampling mode, are the I
following: (a) constant sample pumping rates, (b) sample
pumping rates proportional to stream flow rates, (c) constant
sample volumes and constant time intervals between samples,
(d) constant sample volumes and time intervals between samples
proportional to stream flow rates, (e) constant time intervals
between samples and sample volumes proportional to total stream
flow volumes since last sample, and (f) constant time intervals |
between samples, and sample volumes proportional to total stream
flow rates at time of sampling. The choice of using the grab
sampling method or one of the six compositing sampling methods is
determined by program objectives and the parameters to be sampled. B
o Use of Automatic Samplers
The use of automatic samplers eliminates errors caused
by the human element in manual sampling, reduces personnel _
cost, provides more frequent sampling than practical for I
manual sampling, and eliminates the performance of routine
takes by personnel. Criteria for brand selection of
automatic samplers include evaluations of the intake
device, intake pumping rates, sample transport lines, |
sample gathering systems (including pumps and scoops), power
supplies and power controls, sample storage systems, and
additional desirable features to fit particular sampling I
conditions. There are many comrnerically available automatic
samplers; however, because no single automatic sampler
is ideally suited for all situations, the user should
carefully select the automatic sampler most suited for |
the particular water or wastewater to be characterized.
Precautions must be taken in regard to using certain m
types of samples in potentially explosive atmospheres. I
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o Flow Measurements
An essential part of any water or wastewater sampling
survey as well as a necessary requirement of the National
Pollution Discharge Elimination System (NPDES) permit
program is accurate flow measurements. Flow measurement
data may be instantaneous or continuous.
For continuous measurements, a typical system consists
of primary devices such as weirs and flumes and secondary
devises such as flow sensors, transmitting equipment,
recorders, and totalizers. The improper installation
or design of a primary device or malfunction of any part
of a secondary device results in erroneous flow data.
The accuracy of flow measurement data also varies widely,
depending principally on the accuracy of the primary
device and the particular flow measurement method used.
In any case, measurements should be within +IQ percent
of the true values.
As part of a monitoring activities' QA program, a written
step-by-step procedure for the use of each type of flow
equipment employed by the monitoring activity shall be
available. The write-up is to include the protocol for
installation of the measuring device (if appropriate),
maintenance and verifiction of calibration of the measuring
device in the field. Documentation must also be maintained.
All mechanical and electronic type current meters' calibration
are to be traceable through an unbroken chain (supported
by documentation to some untimate or national reference
standard (i.e., NBS or NOAA).
o Statistical Approach to Sampling
Four factors must be established for every sampling program:
(a) number of samples, (b) frequency of sampling, (c) parameters
to be measured, and (d) sampling locations. These factors
are usually determined in varying degrees by details of
the pertinent discharge permits or are more arbitrarily
set by the program resource limitations. Nevertheless,
the nature of the statistical methods selected and scientific
judgment should be used to establish the best procedures.
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o Special Sampling Procedures I
Special sampling procedures should be employed for
hazardous wastes, toxics, municipal, industrial, and I
agricultural waters, and surface waters as well as
bottom sediments and sludges, and for biological,
microbiological, and radiological studies.
B. Air
o Sampling Site Selection Considerations
I
The need for an air quality monitoring program usually
is related to one or more of the following objectives: I
1. To judge compliance with and/or progress made toward
meeting ambient air quality standards.
2. To activate emergency control procedures that prevent
or alleviate air pollution episodes. _
3. To observe pollution trends throughout a region,
including nonurban areas.
4. To provide a data base for research evaluation of |
effects; urban, "land use, and transportation planning;
development and evaluation of abatement strategies;
and development and validation of diffusion models.
Sampling site and equipment requirements are generally
divided into three categories, consistent with desired
averaging times:
1. ContinuousPollutant concentrations determined with
automated methods and recorded or displayed continuously. I
2. IntermittentPollutant concentrations determined with
manual or automated methods from ii
daily samples on a fixed schedule.
manual or automated methods from integrated hourly or I
3. StaticPollutant estimates or effects determined from
longer-term (weekly or monthly) exposure of qualitative |
measurement devices or materials.
Air quality monitoring sites that employ automatic equip- I
ment to continually sample and analyze pollutant levels
may be classified as primary. Primary monitoring stations
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are generally located in areas where pollutant concentrations
are expected to be among the highest and in the areas of
highest population density and, as such, are often employed
in health effects research networks. In addition, these
stations are designed as a part of the air pollution
episode warning system.
o Network Design Considerations
In designing an air quality monitoring activity, the
following four criteria for locating sites should be
considered, either singly or in combination, depending
upon the objective of sampling:
1. Orient monitoring sites to measure the impacts of
known pollutant emission categories on air quality.
2. Orient monitoring sites relative to population
density to measure receptor-dose levels, both short
and long-term.
3. Orient monitoring sites to measure the impacts of
known pollutant emission sources (area and point) on
air quality.
4. Orient monitoring sites to obtain measurements
representative of areawide air quality.
In order to select locations according to these criteria,
it is necessary to have detailed information of the location
of sources of emission, the geographical variability of
ambient pollutant concentrations, meteorological conditions,
and population density.
o Representative Sampling
Assuring the collection of a representative air quality sample
depends on the following factors:
1. Locating the sampling site and determining network size
consistent with monitoring objectives.
2. Restraints on the sampling site imposed by meteorology.
3. Restraints on the sampling site imposed by local topography,
emission sources, and physical constraints.
4. Sampling schedules consistent with monitoring objectives.
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o Locate Sampling Site and Determine Network Size
Consistent with monitoring objectives previously noted,
networks are designed to meet at least one of four major
objectives. The following tabulation presents examples
of currently implemented networks applicable to each of
these "objectives" categories:
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Objective
Network
Comment
Compliance
monitoring
Emergency
episode monitoring
Trend monitoring
Research
monitoring
SIP (State Imple-
mentation Plan)
SIP/1ocal agency
emergency control
program
NASN (National
Air Sampling
Networks)
CHAMP (Community
Health Air Monitor-
ing Program)
To demonstrate attainment
or maintenance of Air
Quality Standards
To activate immediate,
short-term, emission
controls for prevention
of episodes
To fulfull mandate of
Federal legislation
To determine long-term
pollutant trend in
selected areas with
respect to health effects
o Compliance Monitoring
The information required for selecting sampler location is
essentially the same as that for determining the number of
samplers, i.e., isopleth maps, population density maps,
and source locations. Following are suggested guidelines:
1. The priority area is the zone of highest pollutant
concentration within the region. One or more stations
are to be located in this area.
2. Close attention should be given to densely populated areas
within the region,-especially when they are in the vicinity
of heavy pollution.
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6. Some information of air quality should be available to
I represent all portions of the regions.
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3. For assessing the quality of air entering the region,
stations must also be situated on the periphery of the
region. Meteorological fetors such as frequencies
of wind direction are of primary importance in locating
these stations.
4. For determining the effects of future development on the
environment, sampling should be undertaken in areas of
projected growth.
5. A major objective of surveillance is evaluation of progress
made in attaining the desired air quality. For this purpose,
sampling stations should be strategically situated
to facilitate evaluation of the implemented control
tactics.
Some stations will be capable of fulfilling more than one of
the functions indicated; e.g., a station located in a densely
populated area can indicate population exposures and also document
the changes in pollutant concentrations resulting from control
strategies employed in the area.
o Emergency Episode Monitoring
For episode avoidance purposes, data are needed quickly--
in no less than a few hours after the sensor is contacted
by the pollutant. While it is possible to obtain data
rapidly by on-site manual data reduction and telephone
reporting, there is a trend toward automated monitoring
networks. Obviously, the severity of the problem, size
of the receptor area, and availability of resources influence
both the scope and sophistication of the system.
It is necessary to utilize continuous air samplers because
an episode lasts only a few days and the control actions
taken must be based on "real-time" measurements correlated
with the decision criteria. Based on alert criteria now
in use, 1-hour averaging times are adequate for surveillance
of episode conditions. Shorter averaging times provide
information on data collecting excursions but increase
the need for automation because of the bulk of the data
obtained. Averaging times longer than six hours are not
desirable because of the delay in response this imposes.
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Collection and analysis must be accomplished rapidly if the
data are to be useful immediately. There is no time to
check out the methods, run blanks, calibrate, etc.,
after the onset of episode conditions. In order for the |
instrument to be maintained in peak operating condition,
personnel must be stationed at the sites during the g
episode or automated equipment must be operated that can I
provide automatic data transmission to a central location.
Episode conditions threaten human welfare, and monitoring
sites should be located in areas where this welfare is I
most threatened:
1. In densely populated areas. I
2. Near large stationary sources of pollutants.
3. Near hospitals. V
4. Near high-density traffic interchanges.
5. In homes for the aged.
A network of sites is useful in determining the range of I
pollutant concentrations within an area. Although the most
desirable monitoring sites are not necessarily the most
convenient, consideration should be given, for reasons
of access, security, and existing communications, to the |
use of public building: schools, firehouses, police
stations, hospitals, and water or sewage plants. _
o Trend Monitoring
As typified by the National Air Surveillance Network (NASN),
trend monitoring is characterized by locating a minimal |
number of monitoring sites across as large an area as
possible. The program objective is to determine, in a
broad sense, the extent and nature of air pollution as
well as determine the variation in the measured levels
of atmospheric contaminants in respect to geographic,
socioeconomic, climatologic and other factors. The data
acquired are useful in planning epidemiological investigations I
and also provide the background against which more intensive
community and state-wide studies of air pollution can be M
conducted.
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Urban sampling stations are usually located in the most
densely populated areas of a region. In most regions
there are several urban sites.
Nonurban station loctions include various topographical
categories such as farmland, desert, forest, mountain,
and coastal. The nonurban stations are not specifically
selected to be "clean air" control sites for urban areas,
but they do provide for a relative comparison between
some urban and nearby nonurban areas.
In interpreting trend data one must consider the limitations
imposed by the network design. Even though precautions are
taken to ensure that each sampling site is as representative
as possible of the designated area, it is impossible to
be totally certain that the measurements obtained at a
specfic site are not sometimes unduly influenced by
local factors. Such factors might include topography,
structures, and sources of pollution in the immediate
vicinity of the site, and other variables, the effect of
which cannot always be accurately anticipated but which
should be considered in network design. It must be kept
in mind that when comparisons are made among pollution
levels for various areas, they are valid only insofar as
the sites are comparable.
o Research Monitoring
An example of a research-oriented air quality monitoring
effort is the EPA's Community Health Air Monitoring
Program (CHAMP), which is providing data to develop
criteria for both short- and long-term air quality standards.
Air monitoring networks related to health effects are
composed of integrating samplers for determining
pollutant concentrations for 24 hours, or longer for
developing long-term (_> 24 hours) ambient air quality
standards. These studies require that monitoring points
be located so that the resulting data represent the
population group under study. The monitoring stations
are therefore established in the center of small, well-
defined residential areas within a community. Data
correlations are made between observed health effects
and observed air quality exposure.
Requirements for aerometric monitoring in support of
health studies are:
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1. Station must be located in or near the population under |
study.
2. Pollutant sampling averaging times must be sufficiently I
short to allow for use in acute health effects studies
that form the scientific basis for short-term standards.
3. Sampling frequency should be sufficient to characterize I
air quality as a function of time, usually daily.
4. System should be flexible and responsive to emergency
conditions with data available on short notice.
o Meterological Factors that Affect Representative Sample I
Collection
Meteorology must be considered in determining not only
the geographical location of a monitoring site, but also |
such factors as height, direction and extension of sampling
probes. Meteorological parameters having the greatest _
influence on dispersion of pollutants are the direction,
speed, and variation of wind.
Wind direction provides an indication of the general movement
of pollutants in the atmosphere. Review of available data can |
indicate mean wind direction in the vicinity of the major sources
of emissions. «
The effects of wind speed are two-fold. First, wind speed
determines the travel time from source to receptor. Second,
wind speed affects dilution in the downwind direction,
i.e., concentration of air pollutants is inversely proportional I
to wind speed.
o Topographical Features that Affect Representative Sample I
Collection
The transport and diffusion of air pollutants is complicated I
by topographic features. Minor topographic features may exert I
small influence; major features, such as deep river
valleys or mountain ranges, may affect large areas.
Before final site selection, topography of the area
should be reviewed to ensure that the purpose of monitoring
at that site will not be adversely affected.
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Final placement of the monitor at a selected monitoring
site depends on physical obstructions and activities in
the immediate area, accessibility, availability of utilities
and other support facilities, correlation with the defined
purpose of the specific monitor, and monitor design.
Because obstructions such as trees and fences can significantly
alter air flow, monitors should be removed from such
obstructions. It is important that air flow around the
monitor should be representative of the general air flow
in the area to prevent sampling bias.
Network designers are to avoid sampling locations that
are unduly influenced by down-wash or by ground dust,
such as a rooftop air inlet near a stack or a ground-level
inlet near an unpaved road. In the latter case, either
elevate the sampler intake above the level of maximum
ground turbulence effect or simply place it reasonably
far from the source of ground dust.
o Sampling Schedules Consistent with Monitoring Objectives
Current Federal regulations specify the frequency of
sampling for criteria pollutants to meet minimum SIP
surveillance requirements. Continuous sampling is
specified except for 24-hour measurements of total
suspended particulate matter and 24-hour integrated
values for S02 and N02. The high-volume and gas impinger
measurements are required at least once every six days,
equivalent to about 61 random samples per year. Twenty-
four-hour samples should be taken from midnight (local
standard time) to midnight and thus represent calendar
days to permit direct utilization of the sampling data
with standard daily meteorological summaries.
o Sample Preservation and Holding Times
During and after collection, if immediate analysis is not
possible, the sample must be preserved to maintain its
integrity. Proper handling of the samples helps insure
valid data; consideration must also be given to care of
the field container material and cap material, cleaning,
structure of containers, container preparation for determination
of specific parameters, container identification, and
volumes of samples.
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Sample collection, containers and preservation of industrial
effluents for priority p
specified in Appendix 6.
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Sample collection containers, preservatives and holding |
times for samples collected in the 106, 208, 404(b),
1412 and the Great Lakes National Monitoring Programs
shall be those specified in Appendix 5. I
effluents for priority pollutants protocol shall be those I
Sample collection and preservation protocol for hazardous
waste samples shall be those specified in Appendix 7. g
Sample collection and preservation protocol for ambient
air samples shall be those specified in Appendix 8. I
Sample collection, preservation and holding time protocol
for the 1412 monitoring (public water supply) program
shall be those specified in Appendix 14. |
8.3 Analytical Methodology _
The analytical laboratory provides qualitative and quantitative I
date for use in decision making. To be valuable, the data must
accurately describe the characteristics and concentrations of
constituents in the samples submitted to the laboratory. In many
cases, because they lead to faulty interpretation, approximate or |
incorrect results are worse than no results at all.
Many analytical methods for environmental pollutants have been I
in use for many years and are used in most environmental lab-
oratories. Widespread use of an analytical method in environmental
testing usually indicates that the method is reliable, and
therefore tends to support the validity of the reported test I
results. Conversely, the use of little-known analytical
techniques forces the data user to rely on the judgment of
the laboratory analyst, who must then defend his choice of I
analytical technique as well as his conclusions.
Uniformity of methodology within a single laboratory as well I
as among a group of cooperating laboratories is required to
remove methodology as a variable when there are many data
users. Uniformity of methodology is particularly important
when several laboratories provide data to a common data bank |
(such as STORET) or cooperate in joint field surveys. A
lack of uniformity of methodology may raise doubts as to the
validity of the reported results. If the same constituents I
are measured bv different analytical orocedures within n
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single laboratory, or by a different procedure in different
laboratories, it may be asked which procedure is superior,
why the superior method is not used throughout, and what
effects the various methods and procedures have on the data
values and their interpretations.
Physical and chemical measurement methods used in environmental
laboratories should be selected by the following criteria:
a. The selected methods should measure desired constituents
or environmental samples in the presence of normal inter-
ferences with sufficient precision and accuracy to meet
the environmental data needs.
b. The selected procedures should use equipment and skills
ordinarily available in the average environmental laboratory.
c. The selected methods should be sufficiently tested to
have established their validity.
d. The selected methods should be sufficiently rapid to
permit repetitive routine use in the examination of large
numbers of water samples.
The restriction to the use of EPA methods in all laboratories
providing data to EPA permits the combination of data from
different EPA programs and supports the validity of decisions
made by EPA.
The QAO requires that the methodology be carefully documented.
In some reports it is stated that a standard method from an
authoritative reference was used throughout an investigation,
when close examination has indicated, however, that this was
not strictly true. Standard methods may be modified or entirely
replaced because of recent advances in the state of the art
or personel preferences of the laboratory staff. Documentation
of measurement procedures used in arriving at laboratory data
should be clear, honest, and adequately referenced; and the
procedures should be applied exactly as documented.
Reviewers can apply the associated precision and accuracy of
each specific method when interpreting the laboratory results.
If the accuracy and precision of the analytical methodology
are unknown or uncertain, the data user may have to establish
the reliability of the result he or she is interpreting before
proceeding with the interpretation.
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However, auto analyzer manifolds are to be depicted.
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As part of any monitoring program's quality control program, the I
analytical methodology must be included for review and approval
by the Quality Assurance Office. The format and minimum
requirements for method documentation are listed below:
1. Parameter that the method measures.
2. Principle - A brief description of the method. I
3. Optimum Concentration Range - The analytical range from
the lowest concentration to the highest concentration |
in which a substance is measured. The sample may be
concentrated or diluted so that the substance can be _
detected within this range. I
4. Sensitivity - The slope of a curve of concentration
versus instrument response (such as absorbance).
5. Detection Limit - The lowest quantity which may be
be distinguished from zero with an acceptable degree _
of confidence. I
6. Reference - The source of the analytical method. In
addition all variances of the original procedure are
documented here. |
7. Matrix - The general composition of the sample that the
method is capable of handling, e.g., water (potable,
ambient, wastewater), solids (leachates, sediments,
sludges), air (filter particulates, bubbler solutions,
casette trap). Fluids (solvents, hydrocarbons, oils).
8. Analysis Procedure
a. Description - The analytical procedure is described
for normal conditions. Sample pretreatment (if I
required) and preparation protocols are also
described here. The language used to describe
the method is to be detailed enough (cookbook
fashion) so that a technician with experience in
the respective type of analysis would clearly
understand every step of the procedure. Analytical
techniques that employ a great deal of instrumentation |
such as atomic absorption and automated analysers are
briefly described since instrument manuals are _
available which detail the use of the instrument. I
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b. Instrument parameters - A description of the instrument
and all the instrument settings that are necessary
to setup the instrument for normal conditions.
c. Routine performance tests - A test of the instrument
performance which is separate from a calibration procedure,
and is a gross indication of the instrument's response.
This test is performed and documented each time a
batch of samples is processed or else on a daily
basis. The frequency chosen for instrument
response check is dependent on the analysts'
confidence of instrument stability.
d. Calibration standards - The calibration standards
are described in terms of the range of concentrations
used in the normal procedure and in terms of
composition (preparation of standard solutions)
employed for various matricies.
e. In-house quality control standards - There are
standards which are different from calibration
standards. Quality Control standards are meant
to be a control procedure by which to judge
whether the procedure is in-control or out-of-control
after the various instrument checks have been
satisfied. Wherever used, at least one quality
control standard is determined with each batch of
samples. The information is then documented.
1. one wheel of samples - for auto analyzer
techniques.
2. a number of samples that is determined
continuously without an interuption such as
a coffee or lunch break or a change of
instrument settings - for atomic absorption
techniques, manual techniques, and gas
chromatographic techniques.
f. Data calculations - Describe the computations and
manipulations that must be used to convert raw
data to a final analytical results.
g. Instrument log book - An indication of where the
instrument log book is located. The instrument
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1. Name, Model Number, Serial Number
4. Service record
specified. The use of real sample spikes (positive
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book is to contain, as a minimum, the following I
sections:
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2. Does the identification verify that the instrument
is EPA approved, if required
3. Instrument history
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^ 5. Routine performance test - This section includes
a space for the date, initials of analyst,
comments, and other instruments parameters |
if applicable.
9. Interferences - When interferences are suspected or
indicated by other tests, the specific procedures for
dealing with these interferences are described here.
10. Precision and Accuracy |
The statistical precision and accuracy results for the
parameter generated by the laboratory are to be
documented. I
11. Quality Control
a. Internal Quality Control - In-House Quality Control I
Standards, in addition to being controls, are to be
used as a measure of precision under ideal
conditions. Frequency of use is to be specified.
Reagent Blanks are to be determined to collectively |
check for possible contamination from the sample
container, preservative, glassware, and laboratory
reagents. Frequency of use is to be specified.
The use of replicate analysis of real samples to
measure precision is viewed as a product of the
laboratories. This information is meant for use
in interpreting analytical results and is of some |
use to the laboratory for evaluating the reported
detection limits and detecting possible interferences
that might not be documented in the original method. I
The use of replicates is dependent on the parameter *
(the number of samples with positive values) and the
analytical method. Frequency of use is to be
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or negative) is also dependent on the convenience
with which they fit into the analytical procedure.
Spike are useful for evaluating recovery in
addition to precision. Frequency of use is to
be described.
b. External Quality Control - Participation in various
comparative analytical programs and frequencies
outside of the laboratories are cited here.
8.3.1 Maintenance of Up-To-Date File of Measurement Methods
The Central Regional Laboratory (CRL) currently uses
over 200 approved reference methods to analyze over 500
different environmental pollutants. It is known from recent
on-site inspections that the nine principal State laboratories
in the Region use many analytical methods not used by the CRL
and that they have made "minor" variations in methods in
common use by EPA. The variety of new methods in use by the
other Federal and local laboratories is not yet known, but it
is expected that the total number of agency approved laboratory
methods the QAO will be evaluating will number well over
1,000.
In addition to the laboratory methods, the QAO must monitor the
performance of sampling procedures used by the monitoring programs
conducted by Region V and a wide variety of field measurements.
These include measurement of the common water parameters such
as temperature, flow, dissolved oxygen, pH, etc., as well as
the measurement of air pollutants using both continuous monitors
and grab sampling techniques.
Each of the above methods must be technically evaluated and a
decision made for each method as to whether or not the method is
legally approvable for use in one or more of the many programs
administered by EPA. For example, is the inductively coupled
argon plasma procedure used by the CRL to analyze for metals
significantly different from the approved atomic absorption
procedure to prohibit it use in the analyses of public drinking
water samples. A conservation QAO opinion would answer yes
and therefore require the CRL to either use the manual method
or obtain an alternate test procedure approval pursuant to
the Safe Drinking Water Act. Either action would require at
least 0.5 man years of effort which clearly identifies the importance
of making the correct decision for each method-program combination.
It should be again emphasized that the QAO program requires that
each approved measurement method contain a complete description
of all quality control audit procedures and the frequency and
control limits to be used to insure reliability of reported
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Recommended analytical methodology for priority
pollutants is referenced in Appendix 6. Sample
preparation and analysis for hazardous waste are
those specified in Appendix 7.
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data. Therefore, when a method is approved, the quality j
control program associated with that method will also be
approved.
In summary, this function is not a "bookkeeping" job and is
probably the most difficult work performed by the QAO. It
requires in-depth technical and program skills as well as a
great deal of organizational ability and diplomacy to negotiate |
satisfactory resolutions to the many problems currently facing
the QAO in this area. QAO's initial approach toward completing _
this task is described below.
1. Program Guidelines and Implementation Plans
a. The Reference Methods described in the various EPA
regulations will serve as the basis for all method I
evaluations. Results obtained using the reference
methods will be taken as the officially correct results
even though it is known the result may not always
accurately measure the contaminant concentration of m
interest.
EPA offical analytical methodology for water quality I
measurements are given in Appendix. 9. Radiation
methods are shown in Apendix 10. Ambient air
measurement methods are shown in Appendix 11. Source
air measurements analytical methodology are shown in
Appendix 12. Public water supply measurements _
analytical methodology are shown in Appendix 13. I
Recommended analytical methndnloav for orion'tv
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Analytical measurements for ecological evaluations of _
proposed discharge of dredged or fill material into
navigable waters are listed in Miscellaneous Paper
D-76-17, titled Interim Guidance for Implementation of
Section 404(b)(l) of Public Law 92-500 (FWPCA Ammendments
of 1972), compiled by the U.S. Corps of Engineers. |
A unique number will be given to each method as it is
approved. This will permit the QAO to more easily
use computers to quickly retrieve information related
to the method. The unique number will contain the
following intelligence. I
o Laboratory usi ng method
o Sample type (air, water, sediment, biological)
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o Parameter class (biological, organic, inorganic)
o Parameter (zinc, aldrin, TSP)
o Reference or alternate method
o EPA programs method may be used to support
c. Software programs will be written which will associate
other information with each approved method using the
method number as a cross index. Some of the related
information will be as follows:
o QAO file folder where the "official" method description
is maintained.
o A list of literature references supporting the method.
o The STORET, SARAD, etc., numbers related to the method.
o The appropriate reference method if the method is an
alternate test procedure.
o All quality control audit data.
o A comment space for user remarks pertaining to method
performance.
d. A cross-indexing system will be established in which one
can obtain a list of approved laboratory-method combinations
for each EPA program and a list of programs for which
each laboratory is approved to use each of its
described analytical methods.
e. All approved methods will be reviewed at least once
each year (January - March) to insure that they are
properly classified relative to any regulatory or
technical changes thay may have occurred during the
year.
f. A numerical description of the performance of each
method will be obtained from the group evaluating the
interlaboratory quality control audit data. These
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numbers will be evaluated, interpreted and a description I
will be prepared explaining the performance of the
method for non-technical personnel. It will provide
references to related methods.
g. The out-puts will be:
o An up-to-date list of all approved and some unapproved |
(those being processed, but not formally approved)
methods for making any measurement. Each of these _
methods will have a list of programs which may I
be used to support the reference method, the proper
number to use for storage of results (STORET, SARAD),
the units of measure, the method performance data
(detection limit, working concentration range, |
precision and accuracy) and laboratories approved to
use the method. «
o A copy of any approved method(s) and any approved quality
control program(s).
o An evaluation of methods which were not approved for use I
by the QAO in the proposed program with justification
for non-approval.
h. Relationship to other QAO functions
These official measurement methods will form the
foundation of the QAO program for monitoring data I
reliability. They will be the "contract agreement"
between the QAO and all media offices and will provide
the written communication link for use in legal and
technical challenges. They will provide a management |
structure for evaluating and documenting differences
in method and laboratory performances resulting from
"minor" changes in analytical methods and laboratory
operating procedures.
8.3.2. Alternate Test Procedure Program
The Code of Federal Regulations (40 CFR 136, |
40 CFR 35, 40 CFR 141, etc.), specifies that specific analytical
methods be used to monitor compliance with several regulations «
administered by EPA. In each instance, the regulations provide
a mechanism by which an alternate analytical procedure can be
used in place of the specified reference procedure if it is
first documented that the proposed alternate procedure is
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I the different EPA programs specify different analytical mthods
to be used to analyze for a given contaminant and different
_ mechanisms for obtaining approval to use an alternate test
procedure. This requires EPA to maintain records for all
programs (NPDES, SDWA, etc.)-method (Flame AA, ICAP, Flameless
AA, etc.)-laboratory combinations to insure that reported data
can be used for regulatory purposes.
For Region V, the QAO is responsible for processing all alternate
I test procedure applications in the water program areas. Depart-
ment E, EMSL-RTP, Research Triangle Park, North Carolina, has
sole national responsibility for implementing designated
reference and equivalent methodologies for the air programs
I as specified by 40 CFR 53.1. The Region V alternate test
procedure protocols are described below by program.
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8.3.2.1 Elements of an Application for a National Pollutant Discharge
Elimination System (NPDES) or Section 106 Alternate Test
Procedure
40 CFR 136, "Guidelines Establishing Test Procedures
for the Analysis of Pollutants", specifies approved test
procedures for NPDES self-monitoring and data submitted to
condition an NPDES permit.
Appendix H to 40 CFR 35, specifies approved test procedures
be used by a pollution control agency to show compliance or non-
compliance with an NPDES permit. Other monitoring programs
(ex. - PCB toxic pollutant monitoring) specify the use of 40
CFR 136 test procedures.
40 CFR 136 selects specific documented test procedures from
"Standard Methods", EPA's "Methods for Chemical Analysis of
Water and Wastes", and "ASTM, Part 31", on a pollutant-by-
pollutant basis, for the analysis of NPDES effluents. Based
on the knowledge available to EMSL-Cincinnati, EPA, these
test procedures were selected as the best available test
procedures for effluent analysis - physical, chemical or
microbiological.
40 CFR 136.4 and 136.5 specifies that alternate test procedures
may be used if approval either is obtained from the Regional
Administrtator on a case-by-case basis, or from the U.S. EPA
Administrator on a nationwide basis. Alternate test procedures
are justified by, but are not limited to, increased analytical
performance and increased cost effectiveness to the approved
method(s), or are proposed because they ara promising new
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methodologies. Alternate test procedure applications are I
processed by U.S. EPA if an applicant can justify their use
for NPDES monitoring.
The Regional Administrator approves alternate test procedures on
a case-by-case basis for specific NPDES permits within the specific
U.S. EPA REgion and specific laboratories (public agency and
commercial) receiving NPDES samples from a finite portion of |
an EPA Region. Appendix H to 40 CFR 35 specifically provides
authority to the Regional Administrator for approval of alternate _
test procedures in State laboratories. I
a. NPDES Alternate Test Procedures for Nationwide Use
Contact the Director, Environmental Monitoring and Support
Laboratory (EMSL)-Cincinnati, EPA, Cincinnati, Ohio 45268, |
phone (513)684-7301 or phone FTS 684-7301 for the protocol
concerning alternate test procedures for nationwide use.
b. Elements of an NPDES Alternate Test Procedure Application on a
Case-by-Case Basis
Until and unless printed application forms are made available I
from the U.S. EPA, any person may apply to the Regional I
Administrator in the Region where the discharge(s) occurs,
through the Director of the State Agency having authority
to issue NPDES permits within such State. I
An application should be made in triplicate to the Regional
Administrator and shall: I
o Provide the name, address, and telephone number of the
responsible person, firm or public agency making
application. |
o Identify the pollutant(s) for which approval is sought. _
o Specify the applicability of the proposed test procedure.
Applicability of an alternate test procedure can be
sought for (1) one or more specific NPDES permits (in this
case, the applicable I.D. number(s) must be provided), |
(2) all or certain types of NPDES discharges monitored,
within a geographical area of the Region, by a commercial _
laboratory or by a pollution control agency laboratory I
(State or Federal); or (3) all or certain types of
non-point source monitoring provided by a pollution
control agency laboratory as part of a Section 106
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o Provide a justification for use of the proposed method.
This can be, but is not limited to, increased analytical
performance or cost effectiveness.
o Provide a detailed description of the proposed alternate
test procedure. This should be written in sufficient
detail that another laboratory could reproduce the
applicant's equipment and instrumentation. This is a
necessary part of the application, since final approval
can only be given for a documented test procedure
description. Suggested formats for a detailed description
can be found in "ASTM, Part 31", "Standard Methods", or
EPA's "Methods for Chemical Analysis of Water and Wastes".
o Provide the concentration range of interest for the
pollutant(s) identified in the above item. In the case
of specific NPDES permits, present and expected effluent
limitation concentrations shall be documented. In the
case of non point source waters, the criteria or
standards, which the monitoring program is to assess,
shall be documented.
o Provide the detection limit, and its definition for the
proposed alternate test procedure.
o Provide copies of, or cite reference to any published
studies, if available, on the applicability of the
alternate test procedure to the NPDES effluent types in
question.
o Provide data, using sample aliquots of representative
waste effluents (and untreated or raw wastes, if
appropriate), showing the proposed method yields
results comparable in equivalency and precision to the
reference method, or one of the reference methods,
specified by 40 CFR 136. The comparability data
protocol listed in one of the following two items
will be used.
o For an NPDES discharger, with one to four effluents
of the same waste characteristic, provide comparability
data by the following protocol. Select at least eight
different effluent aliquots, collected over a representative
time period, to provide varying concentration levels of the
pollutant of interest. Determine or measure the
pollutant of interest by the proposed test procedure
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and by a reference method. Specify the reference method I
used. Spike each of 8 aliquots, described above, with
the pollutant of interest. Select spike concentrations
so that the present spike recovery can be calculated I
from the amount of spike added. The chemical compound,
selected to use as a spike material should assess the
complete proposed test procedure or be representative
of the chemical compounds or products of interest in the |
industrial or municipal process of interest. For example,
organic nitrogen or phosphorus compounds should be _
selected as a spiking material for a Kjeldahl nitrogen I
or total phosphorus test procedure in order to include
assessment of the digestion steps. Orthophosphate or
ammonia compounds would only assess suitability of the
final measurement step. After spiking of the waste |
aliquots, determine the pollutant concentrations by
both the proposed method and by the reference method m
of choice. Calculate percent recovery on the basis of I
the amount of spike added. Specify the chemical
compound used as a spike material.
If it is expected that the average percent recovery I
for the spike added will be between 95% and 105%, that
the chemical compound selected for spiking is appropriate,
and that significant concentrations of the pollutant of J
interest is present in the waste effluent aliquots, it
will be unnecessary to analyze spiked samples by the
reference method. If inadequate spike recovery by the I
proposed method is obtained, spike recovery by the
reference method must be provided for comparative
purposes.
If it is expected that there will be undetectable
amounts of the pollutant present, either by the proposed _
method or by the reference method in unsplked samples, I
then equivalency data must be provided using both
spiked and unspiked samples by the two test procedures.
Provide precision data for comparability of the two |
methods, either by analyzing the above eight effluent
aliquots in duplicate by the two methods or by selecting «
a single waste aliquot of representative and detectable I
pollutant concentration and analyzing at least eight
replicate values by each method.
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Tabulate the above date to show equivalency of the
proposed method with a reference method, comparability
or adequacy of spike recoveries and comparability of the
two method's precision and accuracy. Each effluent
aliquot selected for comparability data should be
uniquely identified and described as to appropriate
NPDES Permit Number. All data collected during the
comparability studies must be provided. Provision of
comparability data can not be made on a selective
basis.
o For an NPDES discharger laboratory, State laboratory,
commercial laboratory, or U.S. EPA laboratory seeking
approval for use of an alternate test procedure for a
variety of NPDES permits, for all NPDES permits within
a finite geographical area of EPA, Region V, or for all
NPDES permits for specific industrial or municipal
categories in a finite geographical area of EPA,
Region V, comparability data will be provided by the
following protocol.
Provide equivalency data, by both the proposed and
reference methods, using 15 to 25 aliquots. The aliquots
selected must be representative of the applicability
specified above.
Provide spike recovery data, as appropriate, for the
above 15 to 25 aliquots. Specify the chemical compound
used as a spike material as discussed above.
Provide precision data for comparison purposes,
either by analyzing the above 15 to 25 aliquots in
duplicate by the two methods, or by providing eight or
more replicate analyses of at least three or more of the
15 to 25 aliquots by the two methods.
Tabulate all of the above data for comparative purposes.
Until or unless printed application forms or a
national U.S. EPA policy for a comparability data
protocol is implemented, a case-by-case NPDES alternate
test procedure application in Region V will contain the
above items. It is impossible to specify a comparability
data protocol that is applicable in all situations.
Applicants seeking a case-by-case approval are encouraged
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concentration units.
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to contact the appropriate State pollution control agency |
or the Quality Assurance Office, Region V, EPA, prior to
initiation of comparability studies which do not fit M
the protocols provided in above items. Examples of this I
are proposed test procedures for suspended solids which *
do not allow spiking, pollutants whose test procedure
defines the pollutant (BOD, oil and grease, suspended
solids, fecal coliform, etc.)» and alternative sample I
preservation techniques or holding times. A protocol
for obtaining approval of an alternative preservation
technique or holding time, for limited applicability, I
is described below.
Requests are often made to monitor a certain I
parameter or pollutant in lieu of a pollutant specified
by a NPDES permit (ex. - to monitor chemical oxygen
demand to show BOD permit compliance, after a correlation
factor has been established). It is the policy of the |
Quality Assurance Office, Region V, not to process these
requests as alternate test procedure application.
They should be processed as a request to modify an NPDES I
permit and should be directed to the Enforcement Division,
Region V.
Elements of an NPDES Alternative Sample Preservation or Holding |
Time Application on a Case-by-Case Basis
NPDES alternate test procedure applications are applicable _
to replacement of a preservation technique or to extending I
a holding time specified by a reference method cited by "
40 CFR 136. Applications for such requests are made to
the Regional Administrator in the Region where the discharge(s)
occurs, through the Director of the State agency having |
authority to issue NPDES permits within such State.
An application should be made, in triplicate, to the Regional I
Administrator and shall:
o Provide the name, address and telephone number of the person,
firm or public agency making the request.
o Identify the pollutant(s) for which approval is sought.
o Specify the applicability of the proposed test procedure - i.e.,
specific NPDES Permit Numbers.
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o Provide a justification for use of the proposed preservation
technique - ex. - cost effectiveness.
o Provide a detailed description of the proposed alternative
preservation technique or holding time. This is quite
necessary since final approval can only be given for a
documented test procedure. Suggested formats for a
detailed description can be found in, "ASTM, Part 31",
EPA's "Methods for Chemical Analysis of Water and
Wastes", and "Standard Methods".
o If available, cite references or provide copies of published
studies showing the applicability of the proposed technique.
o Provide data, using sample aliquots or representative waste
effluents (and untreated or raw waste, if appropriate),
showing the proposed preservation technique or holding
time yields results comparable in equivalency (not
biased against the approved technique) and in precision
to the approved preservation procedure.
o For a single NPDES permitted effluent, provide comparability
data by the following protocol.
Select at least fifteen different effluent aliquots,
collected over a representative time period, to provide varying
concentration levels of the pollutant of interest.
Each aliquot of waste should be split into four separate
sample bottles at time of collection.
Two aliquots are to be analyzed by an approved test
procedure using the approved preservation technique. The
remaining two aliquots are to be analyzed, by the same test
procedure, using the proposed preservation technique or
holding time. The test procedure is to be specified.
If the proposed preservation technique uses an extended
holding time, then the maximum holding time, specified
in the proposed preservation techniques detailed test
procedure description, should be used.
Pollutant values should be tabulated for each of the four
waste aliquots along with the corresponding dates of sample
collection, dates of analysis using the proposed technique,
and dates of analysis using the approved preservation technique.
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All analysis values determined should be reported. Data I
can only be discarded on the basis of quality control audit
or control solution values showing a specific set of analyses
to be out-of-control. I
All analyses, using the two preservation techniques, should
be performed in a single laboratory using a single analytical
methodology.
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d. Section 106 of Public Law 92-500 Alternate Test Procedure Program
If approval of a NPDES alternate test procedure is given to I
to a State laboratory, then approval will also be given for
remaining non-point source measurements in the State's Section
106 monitoring program, if so requested. The NPDES alternate
test procedure's working concentration range should be appropriate |
for the needs of the Section 106 program.
If a State requests approval of an alternate test procedure for
non-NPDES monitoring, it may do so without providing complete *
comparability data so long as a documented test procedure
description is provided, there are sufficient published studies
provided to demonstrate its utility, and/or there are sufficient |
intralaboratory quality control data in existence to document
its utility. The Regional Administrator shall determine the m
need for additional comparability data upon the recommendations
of the Quality Assurance Office, Region V.
8.3.2.2 Elements of an Application for a Safe Drinking Water Act 8
(SDWA) Alternate Test ProcedureI
The National Interim Primary Drinking Water Regulations (NIPDWR),
40 CFR 141, implementing the SDWA, specifies test procedures
to use for NIPDWR contaminants. 40 CFR 141.27 states that |
with the approval, both of a primacy State and of the EPA
Administrator, a laboratory may use alternate test procedures.
This authority has been delegated to the Regional Administrator.
A memorandum of March 10, 1977, from the Ofice of Water Supply
(OWS), EPA, specifies the mechanisms for obtaining approval of
SDWA alternate test procedures. Final approval is either I
given by the Regional Administrator on a case-by-case basis
to specific water utilities, and State, Regional EPA, and _
commercial laboratories or by the OWS on a nationwide basis.
The alternate test procedures for nationwide use should be
published in the Federal Register.
The mechanism specified by the March 10th memo is extremly |
cumbersome, but it does designate who has authority for final
decision making. _
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The Regional Administrator is responsible for final determination
of alternate test procedures for approved water utility, State,
commercial, and Regional EPA laboratories. EMSL-Cincinnati and
OWS, both of EPA, are responsible for the determination of
alternate test procedures for nationwide use. Alternate test
procedures approved, as of September 1978, for nationwide
use, are contained in two OWS memorandums of September 1,
1977, and March 9, 1978 (Appendix 15)
If approval of an alternate test procedure has been given by the
Regional Administrator on a case-by-case basis, to a private or
public laboratory for NPDES monitoring, approval for monitoring
of the same pollutant as a SDWA contaminant will also be
given by the Regional Administrator, upon request, so long as
the original NPDES application clearly documents the alternate
test procedure's working concentration range is applicable to
measurement at the Maximum Contaminant Level (M3L) specified
by the NIPDWR.
a. SDWA Alternate Test Procedure for Nationwide Use
Contact the Director, Environmental Monitoring and Support
Laboratory (EMSL)-Cincinnati, EPA, Cincinnati, Ohio
45268, phone (513)684-7301 or phone FTS 684-7301, concerning
the protocol for SDWA alternate test procedures for nationwide
use.
b. Elements ofaSDWA Alternate Test Procedure Application
on a Case-by-Case Basis
Approval of an alternate test procedure can be requested
by a water utility, public, or private laboratory that has
made application for, or has, Interim Laboratory Certification
under an existing State or Federal SDWA laboratory approval
program in Region V, EPA.
Application for use of an alternate test procedure, on a
case-by-case basis, is made in quadruplicate to the Regional
Administrator, through the State water supply program for
those State which have accepted primacy for the SDWA. In
non-primacy States, application is made directly to the
Regional Administrator.
Until or unless printed application forms are made available
from the U.S. EPA on a national basis, a case-by-case
application in Region V, EPA shall:
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o Provide the name, address and telephone number of the
responsible person making application.
o Identify the SDWA contaminant(s) for which approval is |
sought.
o Specify the applicability of the proposed test procedure I
either for a specific utility, or utilities, or for a
specific public agency or commerical laboratory doing
work for utilities.
o Provide a justification for use of the proposed method-
ology instead of a reference methodology.
°Provide a detailed description of the proposed test pro-
cedure. See "ASTM, Part 31", EPA's "Methods for Chemical
Analysis of Water and Wastes", or "Standard Methods", I
for suggested formats.
"Provide data showing the proposed method yields results
comparable in equivalency and precision to a reference |
method or an alternate test procedure approved for
nationwide use, in the concentration range of the _
NIPDWR M3L. Comparability data for 1 to 4 utilities,
of equivalent water characteristics, shall be provided
using the NPDES protocol for eight effluent aliquots.
If approval is sought by a commercial or public agency
laboratory for use for all utilities in a State, then |
the NPDES comparability data protocol using 15 to 25
different water utility aliquots should be utilized. _
Sample aliquots will have to be spiked, at or near the I
contaminant's PCL, and should be measured by both the *
proposed and approved methods. Organo arsenic and
organo mercury compounds shall be used as spiking
compounds for these two contaminants, because their |
reference methods contain specific digestion procedures.
For a wide applicability, sample aliquots, selected
for comparability measurements must be a wide cross-section I
of the potable water in a State. m
o Provide the proposed method's detection limit and precision I
at the contaminant's MCL. The terms detection limit and
precision shall be defined by the applicant.
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8.3.2.3 Processing of Case-by-Case Alternate Test Procedure in Region V
a. A NPDES discharger, water utility, or laboratory should
make application in triplicate, for use of a case-by-case
alternate test procedure, to the Regional Administrator,
through the responsible State authorities having authority
to enforce the National Pollutant Discharge Elimination
System (NPDES) program or the Safe Drinking Water Act
(SDWA). An extra application copy is provided State
authorities. If the State does not have appropriate
enforcement authority, then application is made, in triplicate,
directly to the Regional Administrator.
b. Application for nationwide use of an NPDES or SDWA
alternate test procedure is made directly to the Director,
EMSL-Cincinnati, EPA, Cincinnati, Ohio 45268, in accordance
with EMSL-Cincinnati *s protocols.
c. For a case-by-case application, the State authorities
will forward three copies of the application to the Regional
Administrator with the States' recommendations. The
regulations specify the State agency Director shall
forward this application to the Regional Administrator.
Guidance from the Office of Water Supply (OWS), EPA,
specifies this shall be done by an appropriate State Official.
d. Upon receipt of the application with State recommendations,
(when the application is applicable to a State with delegated
enforcement responsibility), the Regional Administrator
will forward the application, in triplicate, to the Quality
Assurance Office (QAO), Region V, for processing. Upon
receipt of the application, the QAO, Region V, will acknowledge
receipt of the application to the applicant. This starts
the time cycle for action on the request so that a final
determination on the request can be made within 90 days
by the Regional Administrator.
e. If a State with enforcement responsibility for the SDWA
or NPDES program recommends disapproval of the proposed
test procedure, the Regional Administrator shall deny the
application. Copies of this disapproval will be sent to
the appropriate State agency and to its State Laboratory
Director, to the Director, EMSL-Cincinnati, and in the
case of SDWA applications to the Office of Water Supply
(OWS), EPA.
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f. The QAO will review the application for the following:
reflects final authority by the Region and is consistent
with broad national EPA policies.
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o A clear understanding of the applicability of the proposed _
test procedure. I
o A test procedure documented in sufficient detail that another
laboratory could reproduce the results of the applicant's
laboratory. I
o Comparability data in sufficient quantity and consistency with _
the proposed applicability of the alternate test procedure. I
o Consistency with the data quality needs of the SDWA, NPDES
program, and other monitoring programs as appropriate.
If any of the four elements are missing, the QAO will request
the necessary information from the applicant within one
month of receipt of the application. When the applicant J
provides this information to the QAO, a new 90 day cycle
will be initiated.
g. If the application is complete, the QAO will forward a
copy to the Director, EMSL-Cincinnati for his technical
review and recommendations, within two weeks of receipt
of the alternate test procedure application. |
h. At the discretion of the QAO, a copy of the application
will be forwarded to the Water Supply Branch, Region V, I
or to the Enforcement Division, Region V, for their recom-
mendations, if program policies are affected by either
approval or disapproval of the application.
i. Within the 90 day time period, the QAO will receive all
appropriate recommendations and prepare a letter for the _
Regional Administrator's signature to notify the applicant I
of approval of rejection, and in some instances specify *
the additional information which is required to deteremine
whether to approve the proposed test procedure. Copies
of this final determination by the Regional Administrtor I
shall be forwarded to appropriate Regional and State
program personnel, to the State Laboratory Director(s)
of the concerned State(s), to the Director, EMSL-Cincinnati, I
and in the case of SDWA approvals, to the Director, OWS.
The QAO will prepare the final determination letter for
the Regional Administrator so that this determination
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8.3.2.4 Procedures for Equivalent Test Prodcedure Under the Clean Air Act
Methods required by the Clean Air Act are designated as Reference
of Equivalent Methods according to 40 CFR 53.1. The use of
methods which are not so designated must be approved by Depart-
ment E, EMSL-RTP. Procedures for obtaining approval of a
non-designated method are described in 40 CFR 53.4 and 40 CFR
53.14, respectively. These procedures require that any user
modifications which are not reference or equivalence must be
approved by Department E, EMSL-RTP.
8.4 Instrumentation
All monitoring equipment and instrumentation pruchased within
Region V with EPA grant, contract, inter-agency agreement, or
operation funds are to be evaluated and recommended for approval
or rejection by the QAO. For external monitoring projects,
including 201 grants used to purchase monitoring equipment,
the Project Officer will submit the equipment or instrumentation
request and any justifications to the QAO through appropriate
channels for review. Internal office Directors and Branch
Chiefs (Region V) will submit their proposals and justifications
through the appropriate Division/ Office Director to the QAO
through the Surveillance and Analysis Director for review.
As part of the evaluation and approval process the following
minimum points are considered.
o Is there a need, present or future for the item, i.e., does
present or projected regulations specify tests that this equip-
ment will be used for.
o Does the purchaser have equipment in-house that can be
modified or adapted to perform the necessary function at a
lesser cost.
o Wi11 the purchaser have the necessary auxiliary in-put,
eg., if G.C. - Mass spectroscopy unit is requested, will
library facilities be available.
o Are there technically competent personnel available to
operate the equipment. If not, what plans are available for
hiring or training such personnel.
The QAO will forward an official recommendation of approval
for funding/purchase or a recommendation for not funding/purchase
to the appropriate project officer, Division/Office Directory
through appropriate channels. In the case of not recommending
funding/puchase a justification is also provided.
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8.5 Calibration and Standards |
Calibration procedures require the application of primary or
secondary standards. The standards used, whether they are _
apparatus or reagent standards are to be certified as being I
traceable to standards of the National Bureau of Standards,
or other recognized fundamental standard. This type of trace-
ability is possible when standards are generated in the laboratory.
Regardless of the type of calibration equipment or material, |
an effective QA program requires accuracy levels of these
materials that are consistent with the method of analysis. _
The calibration policies and procedures outlined in 8.5 apply I
to all measuring and test equipment/instrument associated *
with a monitoring activity, including:
o Sampling equipment at sampling stations |
o Analytical equipment/instruments in the laboratory M
o Flow measuring devices (eg., current meters, rotameters) ,
volume (eg., dry gas meters), pressure, vacuum and temperature
measurement equipment at the sampling station and in the laboratory. I
As part of a monitoring activity's (Federal, State, local
agency, contractor or grantee) QA program a written step-by-step
procedure for a frequency for calibration of measuring and test
equipment/instruments and use of calibration standards is to be
provided, in order to eliminate possible measurement inaccuracies
due to difference in techniques, environmental conditions, choice I
of higher level standards and compliance with Agency regulations
(eg., 40 CFR Part 58, Appendix A and B). As a minimum, these
procedures are to include the following:
1. The specific equipment or group of equipment (instruments)
to which the procedure is applicatable. Equipment of _
the same type, having compatable calibration points, I
environmental conditions, and accuracy requirements, may be
serviced by the same calibration procedure.
2. A brief description of the scope, principle, and/or |
theory of the calibration method.
3. Fundamental calibration specification, such as calibration I
points, environmental requirements, and accuracy requirements.
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4. A list of calibration standards and accessory equipment
required to peform an effective calibration. Manufacturer's
name, model number, and accuracy should be included as
applicable.
5. A complete procedure for calibration arranged in a
step-by-step manner, clearly and concisely written.
6. Calibration procedures are to provide specific
instructions for obtaining and recording the test data,
and include data sheets that are to be used.
7. A detailed documented sample of computations for any
calibration procedure that requires statistical analysis of
results.
8. All field and laboratory calibration are to be traceable
through an unbroken chain (supported by reports or data
sheets) to some ultimate or national reference standard.
9. An up-to date- report for each calibration standrd used in
the calibration system is to be made available for review
during the QAO's audit or on-site system evaluation of
any monitoring activity in Region V, funded by EPA.
All equipment past due for calibration should be removed
from service either physically or, if this is impractical, should be
impounded by tagging or other means.
The monitoring activity's quality control official or other
individual delegated quality control responsibility (e.g., Lab-
oratory Section Chief) has day-to-day responsibility to ensure
that the monitoring activity maintains the required accuracy
in the calibration program.
The QAO will evaluate the monitoring activity's on going
calibration and standards activity as part of the audit and on-site
evaluation process to ensure valid data is being produced. Problems
will be identified and recommendations for corrective action provided.
The QAO cannot validate data that is suspect. Follow-up to validate
and approve correction actions will be QAO's responsibility.
8.6 Preventive Maintenance and Inspections
As defined here, preventive maintenance is an orderly program
of positive actions (equipment cleaning, lubricating, reconditioning,
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adjustment and/or testing) for preventing failure Of monitoring I
systems or parts thereof during use. The most important effect
a good preventive maintenance program has is to increase measure-
ment system reliability and thus increase data completeness. I
Conversely, a poor preventive maintenance program will result
in increased measurement system downtime (i.e., decrease in
data completeness) and in increased unscheduled maintenance
costs; and may cause distrust in the validity of the data. In |
ambient air monitoring, data completeness criteria are used to
validate data. _
A responsible individual (i.e., field section Chief, laboratory '
Section Chief, QC Officer) is required to prepare and implement
a preventive maintenance schedule for all equipment and measuring
systems, as part of the monitoring activity's total QC program. |
The planning required to prepare the preventive maintenance
schedule will have the effect of: _
1. Highlighting that equipment or those parts therof that are
most likely to fail without proper preventive maintenance.
2. Defining a spare parts inventory that should be maintained |
to replace worn-out parts with a minimum of downtime.
A specific preventive maintenance schedule is to relate to the I
purpose of testing, environmental influences, physical location
of equipment, and the level of analyst skills. Checklists are
to be used as documentation for listing specific maintenance I
tasks and frequency (time interval between maintenance). In
some instances, if calibration tasks are difficult to separate
from preventive maintenance tasks, a combined preventive
maintenance - calibration schedule is advisable.
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A record of all preventive maintenance and daily service checks _
are to be maintained. An acceptable practice to follow for I
recording completion of task is to maintain a preventive maintenance
calibration multiple copy log book. After tasks have been completed
and entered in the log book, a replicate copy of each task is
removed by the individual performing the maintenance - calibration |
task and forwarded to the appropriate supervisor and QC Officer
for review and conformance with monitoring activity's preventive .
maintenance protocol. The log book is stored by the instrument I
for future reference. The QAO will review these log books
during the audit or on-site systems evaluation activity for
deficiencies.
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8.7 Quality Control Procedures
Assuming that all basic variables pertaining to laboratory
services (i.e., instrumentation, glassware, reagents, solvents,
gases, etc.) are under control, that approved methods are being
used, and the complete system is initially under quality control,
valid precision and accuracy data must initially be developed
for each method and analyst. Then, to insure that valid data
continue to be produced, systematic daily checks must show that
the test results remain reproducible, and that the methodology
is actually measuring the quantity in each sample. In addition,
quality control must begin with sample collection and must not
end until the resulting data have been reported. Quality control
of analytical performance within the laboratory is thus but one
vital link in generation and dissemination of valid data for
agency use. Understanding and conscientious use of quality
control among all field sampling personnel, analytical personnel,
and management personnel is imperative. Region V's procedures
are outlined in the following Sections (8.7.1 and 8.7.2).
Management of QC procedures (how and by whom) is described in
Section 10.2.
8.7.1 Intra-Laboratory Quality Control Procedures
The purpose of intralaboratory QC programs is to identify the
sources of measurement error and to estimate their bias (accuracy)
and variability (repeatability and replicability). For manual
measurement methods, bias and variability are determined separately
for sample collection and analysis and are combined for determination
of total method bias and variability. For continuous methods,
total method bias and variability are determined directly.
Some of the potential error sources are the operator or analyst,
equipment, the calibration, and the operating conditions. The
results may be analyzed by making comparisons against each
other and/or against reference standards. To maintain a known
level of competence in daily activities, quality control must
be implemented in the field and at the bench, using a system of
checks to determine the accuracy and precision of results and
the performance of measurement systems and operators. Intra-
laboratory quality control is a continuing activity to insure
the output of data of known quality. The specific objectives
are to devise a program that:
o measures and control the precision of procedures and instruments.
o measures and control the accuracy of analytical results.
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o documents, on a continuous basis, the performance of systems
analysts and operators. I
o establishes training needs. M
o identifies weak measurement methodology and provides feedback
to the Quality Assurance Office, where an evaluation can be
made of the findings and the appropriate EMSL group notified I
so method revisions and/or modifications can be made.
In Region V quality control charts are to be the foundation
of the laboratory's inter!aboratory quality control programs. |
One form of quality control showing trends is the summation of
the differences squared for replicate samples. Additional _
control charts are recommended where standard deviations are I
(d = Vd2/k) for use on a daily basis to establish rapidly if
an analysis is out of control on a given day. Once precision
and accuracy data are available on the method and the operator/
analyst, systematic daily checks are necessary to ensure that |
valid data are being generated. From these daily precision and
accuracy data, quality control charts can be constructed and _
maintained to determine when the method used is producing valid I
data, when the data are questionable, or when a trend is detected "
which must be investigated and corrected.
Several techniques are available for constructing quality control |
charts and plotting subsequent data. The two techniques currently
used by EPA are the Shewhart technique and/or Cumulative-Summation f
technique. These techniques are depicted in (EPA Publications) I
EPA-600/4-79-019, Handbook for Analytical Quality Control in Water
and Wastewater Laboratories, March 1979, and Quality Assurance
Handbook for Air Pollution Measurement Systems, Volume I I
(EPA-600/9-005), Volume II (EPA-600/4-77-0272a) and Volume III
(EPA-660/4-77-027b). For both techniques, precision control
charts are constructed from duplicate sample analyses, and
accuracy control charts are constructed from spiked sample I
analysis, utilizing standard reference materials (SRM). SRM's
are substances which qualify as absolute quantities against
which other like substances can be calibrated or measured. The I
SRM, typically produced by organizations like the National
Bureau of Standards (NBS), is used to prepare standard reference
standards (SRS) for routine laboratory and field use.
SRS (also referred to as spiked samples) are preparations of known
amounts of standard reference materials added to an actual environ-
mental samples which has been previously analysed. The amount I
of the substance found in the sample is a "true" indication of
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the accuracy of the method for a given measurement. The use of
the standard reference samples measures the extent of interferences
which cannot be obviated.
Following normal procedures, the control chart must indicate
the conditions under which it was developed; i.e., laboratory name,
parameter, method of analysis, date of preparation, and any other
information unique to the initializing data such as range of
concentration and identification of analyst(s)/operator. A
control chart is not generally applicable under other conditions.
To verify the accuracy and precision of control charts, the
initializing data should be checked to be sure that none of the
values exceeds these new control limits. In addition, if its
distribution is proper, about 68 percent of the initializing
data should fall within the interval average percent recovery
plus or minus 2 times the standard deviation for percent recovery.
There is a question of validity of the control chart if less
than 50% of the initializing data falls within this interval.
In application of the accuracy control chart, either of the
following two conditions indicates an out-of-control situation.
a. Any point beyond the control limits.
b. Seven successive points on the same side of the interval
average percent recovery of the central line of the
completed control chart.
When an out-of-control situation occurs, analyses shall be stopped
until the problem has been identified and resolved, after which the
frequency should be increased for the next few percent recovery QC
checks. The problem and its solution must be documented, and all
analyses since the last in-control point must be repeated or discarded.
For some parameters it may be necessary to construct low level and
moderate to high level accuracy QC charts for each standardization
concentration level sample.
In application of the precision control chart, the chart should
be updated periodically as additional, or more current, data
become available, or whenever the basic analytical system undergoes
a major change. If any difference between duplicate analyses
exceeds the critical-range value for the appropriate concentration
level, then analyses should be stopped until the problem is
identified and resolved, and the frequency is to be increased
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for the next few precision checks. After resolution, the problem I
and its solution must be documented, and all analyses since the
last in-control check must be repeated or discarded.
Once the quality control charts have been developed and put in B
place, the normal day to day working routine requires the following:
o A new standard curve should be established with each new |
batch of reagents, using at least seven concentration levels.
The number of level in continuous monitors is 3 levels within _
range. I
o With each batch of analyses (10 to 20% of the time), the
following tests are to be run:
1. One blank on water and reagents.
2. One midpoint standard.
3. One standard reference standard (spike) to determine
recovery.
4. One set of duplicate analysis.
The results from 2 through 4 are to be compared with previous I
in-control data by using the-protocol specified above (for a
detailed protocol description refer to Section 6.3 of Chapter 6
of EPA Publication 600/4-79-019).
The following protocol is to be implemented to indisputably
establish the validity of data for each parameter from water
and wastewater projects: |
In the following protocol the symbols used represent the
results of analysis according to the scheme: I
AI = first replicate of sample A
A£ = second replicate of sample A |
B = sample taken simultaneously with sample A _
Bsp = field spike into sample B "
= laboratory spike into sample B
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DF = field spike into distilled water
D[_ = labortory spike into distilled water
T = true value for all spikes
The laboratory spikes B$L and DL are the only analyses that may
not be necessary. All other analyses must be done simultaneously.
Field personnel should perform the following steps for quality
assurance.
a. Take independent simultaneous samples A and B at the same
sampling point. Depending on the parameter, this might
involve s-ide-by-side grab samples or composite samplers
mounted in parallel.
b. Split sample A into the equal-volume samples Aj and A2.
c. Split sample B into equal volumes and add a spike T to
one of them; the latter sample becomes sample B$p.
As with all spikes, the addition of T should approximately
double the anticipated concentration level.
d. Add the same spike T to a distilled water sample furnished
by the alboratory and designate this sample as Dp.
These QC samples must be treated in the same way as routine
samples; i.e., the volume, type of container, preservation,
labeling, and transportation must be same for all.
The laboratory pesonnel should perform the following steps for
quality assurance:
a. Analyze the blank and midpoint standard recommended in
the normal day-to-day working routine. If results are
unsatisfactory, resolve problems before continuing.
b. Analyze sample Dp. If the percent recovery of T is
unsatisfactory (see accuracy protocol), create a
similarly spiked, distilled-water sample D[_ and analyze
to test for a systematic error in the laboratory or
fundamental problems with the spike. If the percent
recovery of T from D[_ is satisfactory, any systematic
error occurred before the samples reached the laboratory.
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c. Analyze samples B and B$F- If B is below the detection I
limit, or if B is greater than 10T or less and O.IT,
disregard the remainder of this step and proceed to
step d. If the percent recovery of T from B$F is I
unsatisfactory (see accuracy protocol), spike an aliquot
of sample B the same way in the laboratory so that a
similar recovery can be anticipated. Analyse this sample
BSI to test for immediate sample interferences or a |
bad background result B. If the percent recovery from
BSL is satisfactory, then the interference must require
a longer delay before analyses, or other special conditions I
not present in the laboratory, in order to have a
noticeable effect upon recovery of the spike.
d. Analyze Aj and l\2' ^ tne absolute (unsigned) difference |
between these results exceeds the critical value (see
precision protocol), then test of precision is out of control. g
e. Calculate the absolute difference between AI and B. If *
it is unsatisfactory (see precision protocol), the field
sampling procedure did not provide representative samples.
If initial results at each of the laboratory steps were satisfac-
tory, then the validity of the related data has been indisputably M
established. If results at any step are unsatisfactory, resolution I
depends upon the problem identified. Laboratory problems may
just require that the analyses be repeated, but field problems
will usually require new samples. Figure 8.7.1 is intended to I
clarify the interdependence of the preceeding laboratory steps
b through e.
In figure 8.7.1 it must be noted that there is no way to identify |
additive sample interferences; i.e., those that have an equal effect
upon the background-pi us-spike results (B$p or B$[_) and the background
result B. Recovery of a spike will not show such interferences. I
Problems causing systematic errors that may occur in the field
include the following:
a. Contaminated preservative, distilled water, or containers
b. Contamination by sampling personnel I
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c. Deterioration through excessive holding time or use of an
ineffectual preservation technique
d. Use of a bad field spiking procedure
8.7.1.2 Intra-Field Quality Control Procedures
Quality control programs for sampling equipment and for field
measurement procedures (of such parameters as temperature,
dissolved oxygen, pH and conductance) are necessary to insure
data of the highest quality. A field quality control program
administered by a quality assurance coordinator should contain
the following documented elements:
a. The analytical methodology; the special sample handling
procedures; and the precision, accuracy, and detection
limits of all analytical methods used.
b. The basis for selection of analytical and sampling
methodology. For example, all analytical methodology
for NPDES permits shall be that specified by the Agency
or shall consist of approved alternative test procedures.
Where methodology does not exist, the quality assurance
plan should state how the new method will be documented,
justified, and approved for use.
c. The amount of analyses for quality control expressed as
a percentage of overall analyses, to assess the validity
of data. The complete quality control program is to
specify 5% as a minimum for time assigned to field QC.
The plan should include a shifting of these allocations
or a decrease in the allocations depending upon the degree
of confidence established for collected data.
d. Procedures for the recording, processing, and reporting
of data; procedures for review of data and invalidation
of data based upon QC results.
e. Procedures for calibration and maintenance of field
instruments and automatic samplers.
f. A performance evaluation system, administered through the
quality assurance coordinator, allowing field sampling
personnel to cover the following areas:
(1) Qualifications of field personnel for a particular
sampling situation.
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(2) Determination of the best representative sampling
site.
(3) Sampling technique including location of the points |
of sampling within the body of water, the choice of
grab or composite sampling, the type of automatic _
sampler, special handling procedures, sample I
preservation, and sample identification.
(4) Flow measurement, where applicable.
(5) Completeness of data, data recording, processing,
and reporting.
(6) Calibration and maintenance of field instruments and
equipment.
(7) The use of QC samples such as duplicate, split, or H
spiked samples to assess the validity of data.
g. Training of all personnel involved in any function |
affecting the data quality.
Quality assurance in sample collection is to be implemented to I
minimize such common errors as improper sampling methodology,
poor sample preservation, and lack of adequate mixing during
compositing and testing.
At selected stations, on a random time frame, duplicate samples are
collected from two sets of field equipment installed at the site, _
or duplicate grab samples are collected. This provides a check
of sampling equipment and technique for precision.
A representative subsample from the collected sample is removed
and both are analyzed for the pollutants of interest. The samples I
may be reanalyzed by the same laboratory or analyzed by two
different laboratories for a check of the analytical procedures. M
Known amounts of a particular constituent are added in the field to
an actual sample or to blanks of deionized water at concentrations
at which the accuracy of the test method is satisfactory. The
amount added and frequency is coordinated with the laboratory. I
This method provides a proficiency check for accuracy of the
analytical procedures.
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Acids and chemical preservatives can become contaminated after a
period of use in the field. The sampler should add the same
quantity of preservative to some distilled water as normally
would be added to a wastewater sample. This preservative blank
is sent to the laboratory for analysis of the same parameters
that are measured in the sample and values for the blank are
then subtracted from the sample values. Liquid chemical
preservatives should be changed every 2 weeks, or sooner,
if contamination increases above predetermined levels.
A minimum of seven sets each of comparative data for duplicates,
spikes, split samples, and blanks should be collected to define
acceptable estimates of precision and accuracy criteria for data
validation of field parameters.
Protocol is to be developed and implemented for calibrating all
field analysis test equipment and calibration standards to include
the following: (a) calibration and maintenance intervals, (b) listing
of required calibration standards, (c) environmental conditions
requiring calibration,-and (d) a documented record system.
Written calibration procedures should be documented and should
include mention of the following:
a. To what tests the procedure is applicable.
b. A brief description of the calibration procedure.
c. A listing of the calibration standard, the reagents, and
any accessory equipment required.
d. Provisions for indicating that the field equipment is
labeled and contains the calibration expiration date.
,7.1.3 Additional Intralaboratory Quality Control Procedures for
Specific Groups of Parameters
a. Microbiology intralaboratory quality control.
A quality assurance program for microbiological analyses must
emphasize the control of laboratory operations and analytical
procedures because the tests measure living organisms that
continually change in response to their environment.
Further, because true values cannot be provided for the
microbial parameters, microbiologists do not yet have the
advantages of analytical standards, QC charts, and spiked
samples available to other disci plies for measurement of
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accuracy. Because known values cannot be applied, it is
important that careful and continuous control be exerted
over sampling, personnel, analytical methodology, materials,
supplies, and equipment.
A documented inter!aboratory QC is to address the following
areas as a minimum:
o An Operating Manual shall be prepared which describes the
sampling techniques, analytical methods, laboratory operations,
maintenance and quality control procedures. Specific details
are given on all procedures and quality control checks made
on materials, supplies, equipment, instrumentation and
facilities. The frequency of the checks, the person
responsible for each check (with necessary back-up assignments)
the review mechanism in the QC program to be followed, the
frequency of the review and the corrective actions to be
taken are specified. A copy is provided to each analyst.
Part V of EPA Publication EPA-600/8-78-017 describes the
normal day-to-day microbiology inter!aboratory QC routine,
to be implemented by Region V microbiology laboratories.
A record is to be maintained of the daily QC checks and
procedures, if there is no proof of performance, and
evidence for future reference, for practical purposes,
no QC program is in operation.
o A Sample Log shall be maintained which records, I
chronologically, information on sample identification
and origin, the necessary chain of custody information,
and analyses performed.
o A Written Record shall also be maintained of all analytical
QC checks: positive and negative culture controls, sterility
checks, replicate analyses by an analyst, comparative data I
between analysts, use-test results of media, membrane
filters and laboratory pure water, replicate analyses done
to establish precision of analysts, or of methodology used
to determine non-compliance with bacterial limits established |
by Agency regulations.
Aquatic Biology Inter!aboratory Quality Control I
Interlaboratory QC procedures for aquatic biology programs
are fully described in EPA Publication, EPA-679/4-73-001.
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An operating manual shall be prepared, addressing the
following essential elements as a minimum:
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1. An understanding and acceptance of the importance
of quality control (QC) and a commitment on the
part of the biology staff to fully integrate QC
practices into field and laboratory operations.
2. Staff needs with adequate formal training and
experience and proper specialization to meet
program needs.
3. Adequate field equipment, storage and laboratory space,
instrumentation, and taxonomic references.
4. Protocol for preparation and design of field and
laboratory studies.
5. Documentation of approved methodology, where available,
and protocol for consideration of the tehcnical
defensibility of the methods and their application.
6. Protocol for use of replication in sample collection
and analyses where feasible, and determination of the
accuracy and precision of the data.
7. Protocol for frequent calibration of field and
laboratory instruments.
8. Protocol for proper sample identification and handling
to prevent mi sidentification or intermixing of samples.
9. Protocol for blind, split, or other control samples
to evaluate performance.
10. Procedures for development and regular use of in-house
reference specimen collections, and use of outside
taxonomic experts to confirm or provide identifications
for problem specimens.
11. Procedures for meticulous, dual-level review of the
results of manual arithmetical data manipulations and
transcriptions before the data are used in reports
or placed in BIO-STORET.
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Organic Chemistry Interlaboratory Quality Control |
Most of the quality control program described above in
Section 8.7 of this document cannot easily be adapted to _
the methods for organic compounds. Therefore, the Agency I
has developed a series of tests and protocols whose purpose
is to describe the performance of the computerized gas
chromatography - mass spectrometry systems and the analysts(s).
The complete protocol procedure is listed in Appendix 16. I
A summary of these performance tests follows:
I. Spectrum Validation Test - Uses decafluorotriphenyl I
phosphine (DFTPP) to deteremine whether the system gives
a 70 ev electron ionization fragmentation pattern similar
to that found in the historical mass spectrometry data I
base, and the required mass resolution and natural
abundance isotope patterns. The spectrum of DFTPP must
meet the criteria given in Table 2 of Appendix 16.
II. System Stability Test - Uses DFTPP to test moderate term
(20-28 hours) system stability. The criteria given in _
Test I must be met. I
III. Instrument Detection Limit Test - Uses DFTPP to measure the
full and valid spectrum detection limit at a defined and
tolerable noise level. At a signal/noise = 5, the |
required instrument detection limits are 50 nanograms
for systems used in the anlaysis of industrial or municipal _
wastes, and 30 nanograms for systems used in the analysis I
for ambient or drinking water.
IV. Saturation Recovery Test - Uses DFTPP and _p_-bromobiphenyl
to simulate a frequently encountered situation with I
real samples. The spectrum of DFTPP, measured within
two minutes after the elution of a 250 fold excess of
j>bromobiphenyl, must not contain significant contributions I
from the ions attributable to j>bromobiphenyl. m
V. Precision Test - Uses a variety of typical environmental I
pollutants to determine precision from filling a syringe
to peak integration. The mean relative standard deviation
for the compounds used in the test which elute as narrow
peaks must be 7% or less using either peak areas in |
arbitrary units or ratios of peak areas. For broad
peaks the mean relative standard deviation must be 13%
or less.
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VI. Library Search Test - Uses data from Test V to evaluate the
speed and completeness of the minicomputer library search
algorithm. The mean search time, including background
subtraction, must be one minute or less, and all test
compounds must be identified as most probable except
isomers with very similar spectra should not be counted
as incorrect.
VII. Quantitative Analysis with Liquid-Liquid Extraction - Uses
a variety of environmental pollutants to measure quantitative
accuracy and precision of the total analytical method.
The mean of the means of the percentages of the true
values observed must be in the 68-132% range with a
mean relative standard deviation of 38% or less using
either internal or external standards. This test also
evaluates laboratory performance.
VIII. Quantitative Analysis with Inert Gas Purge and Trap - Uses a
variety of compounds to measure quantitative accuracy and
precision of the total analytical method. The mean of
the mean method efficiencies must be 70% or more.
Chloroform efficiency must exceed 90% and all compounds
must exceed 30% efficiency. The spectrum of j>bromofluoro-
benzene must meet the criteria given in Table 7, Appendix 16.
The mean of the means of the percentages of the true
values observed must be in the range of 90-110% with a
mean relative standard deviation of 19% or less using
either internal or external standards.
IX. Qualitative Analysis with Real Samples - Uses a real sample
to evaluate the ability of the system to deal with real sample
matrix effects and interferences. All compounds must
be correctly identified except isomers with nearly
identical mass spectra should not be counted as incorrect.
This test also evaluates laboratory performance.
X. Solid Probe Inlet System Test (Optional) - Uses cholesterol
to evaluate the spectrum validity achievable with a
solid probe inlet system. The spectrum of cholesterol
must meet the criteria given in step three of the test.
The performance tests are intended for use in the evaluation
of the system initially and on a long term basis. All
tests are to be initially performed with correction being
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made to meet the criteria established in Appendix 16 for I
the respective test. The results and corrections are to be
documented.
Test I performance is to be revalidated on a daily basis.
Test IV, V, VII, VIII, and IX performance are to be revalidated
on a specified frequency identified in the documented intra- I
laboratory QC protocol.
The normal day-to-day (£ routine is divided into three separate
categories. Data generated from each category is documented. |
Problems identified must be corrected and documented. When
out of control situations occur, analyses shall be stopped _
until the problem has been identified and resolved. I
The first category represents the determination of purgeable
compounds. This determination is performed in a closed
analytical system; the complete analysis can be performed |
in 1 h; and the number of theoretically possible interferences
is somewhat limited. The second category represents liquid/liquid
partition methods in a regulatory situation. Here a very I
limited number of compounds are being measured; there is a
high occurrence of positive results; and it is important to
establish that the method works satisfactorily on the particular
sample matrix. The third category represents liquid/liquid I
partition methods in a monitoring situation. Here a large
number of compounds are often being measured simultaneously;
there is a low occurrence of positive results; and each sample I
matrix may be different. Quality assurance is aimed at
establishing that the laboratory is using the method correctly.
The purgeable methods are unique among organic methods because
the standards are treated in exactly the same way as the samples,
and there is no inherent method bias. The methods are amendable
to a variety of quality assurance programs. The approach |
that has been found applicable to all types of samples and
provides the maximum data for the expended effort consists m
of the addition of one or more internal standards to the I
matrix before purging. Data generated in this program
provide a continuous monitoring of the equipment and establishes
matrix applicability for the test.
For liquid/liquid extraction methods in a regulatory situation,
the emphasis is placed on duplicates and dosed samples. Both
field duplicates and laboratory duplicates are used in the
program to establish sampling and subsampling validity.
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The dosing of samples to establish method accuracy for the
matrix is an integral part of this program. Where the
analytical program will extend over a long period of time
the construction of control charts is recommended.
When the liquid/liquid extraction methods are used for monitoring,
the emphasis is placed on an external control series. A standard
laboratory matrix is developed. With each series of samples the
matrix is dosed and analyzed with the samples. Data generated
over a period of time can be used to monitor the performance
of the equipment and the analyst, with relatively tight
specifications to define problems that arise. Control
charts can be constructed to alert the analyst to problems,
but there is no provision for rejection of results for
samples of this type.
8.7.2 Inter-laboratory Quality Control Procedures
An inter-laboratory quality control program serves to select and
evaluate methods, characterize their precision and accuracy, and
provide data for evaluating both laboratory and analyst performance.
Specific objectives of this program are to:
o Measure the precision of reproducibility of methods of analysis
within various programs.
o Identify interference in different sampling environments.
o Measure the precision and accuracy of results between laboratories.
o Provide a mechanism for evaluation and/or certification of lab-
oratories and analysts.
o Detect weak, improper, or impractical methodology.
o Detect training needs and upgrade laboratory performance.
o Assist laboratories or programs in obtaining new resources.
The inter-laboratory quality control program is referred to as the
Accuracy and Performance Audit* Programs by the Quality Assurance Office,
Region V. This program was briefly referred to in Section 4.2.1.
*Audit - A check made by the QAO or its representative to determine the
reliability of a specific step in a measurement. For example, a
check on the flow of a Hi-Vol air sampler, the sensitivity of a
spectrometer detector and the ability to analyse a blind unknown
sample are all audits.
*System Evaluation - An on-site inspection and review of the total quality
assurance and quality control program. The inspection will be
made by the QAO or its representative.
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Standards. Materials which have assay values which have been
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8.7.2.1 Management of the Accuracy and Performance Audit Programs
The number of programs in water, waste, air and special projects
are several. The number of measurement parameters which are
utilized in these several programs are numerous. QAO presently
manages this program by manual means. All data is evaluated
manually, which requires a considerable amount of time. As soon
as the last Milestone on page 7 of this document is met the
QAO will manage an audit program utilizing ADP programs which will |
provide the needed level of audits that will assure quality data
adequate for the requirements of the data user. _
The areas of activities which are covered under this audit program
are described below:
1. Audits are to be performed according to frequencies and |
procedures required by Federal Regulations, EPA Guidelines
or Region V Policy (e.g., air audits shall conform to the _
requirements of 40 CFR Part 58, Appendix A and B). The scope I
of audit must be determined for each measurement parameter *
(analyte). A performance audit for the measurement of a
given analyte in drinking water would be carried our by mailing
a reference sample to a laboratory. The reference sample
would contain the analyte in a concentration known to QAO,
but unknown to the analyst. The analyte would be measured m
and the value reported back to QAO. A similar type audit I
would be performed for sewage treatment plants, laboratories
analyzing water from lakes and streams, etc. On the other
hand, an audit of a Hi-Vol Sampler would require an individual I
going to a sampling site, measuring flow rates using two or I
more reference plates and examine the equipment for maintenance
and operating conditions, recording temperature, pressure and
other information. jj
2. Audit materials are available from EMSL-Cinci nnati, EMSL-RTP,
EMSL-LV and commercial sources. Audit materials may be prepared I
as needed by QAO in conjunction with Central Regional Laboratory
and/or contractors. A repository of reference materials will
be maintained by QAO for special substances, substances obtained
by contract and from other sources when not available from |
EMSL. A central reference file will be developed which can
be accessed by Automatic Data Processing (ADP). This file _
will give the facility providing the reference material, the I
concentration or weight per unit and method used to establish "
reference value. Reference materials will be referenced to the
highest standard available, preferably to National Bureau of
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verified by Best Available Technology (BAT) are referred to
as SRM's and those which have been assayed by NBS are NBS-SRM.
Federal Regulations and EPA Guidelines will be followed in
determination of the appropriate SRM. Other materials will
be measured by BAT and designated as reference samples.
3. Studies will be conducted as specified in QAO's program plan
to accomplish certain objectives relative to audits, reference
materials, and methods. Determination of the "true value" of
an analyte is at time tenuous. Only an estimate of the "true
value" can be made for some analytes. The determination or
estimation of the value for a reference material will be
derived from collaborative testing. These studies will use
data from studies such as:
a. The methodology within the International Joint Commision
(IJC) group of analytic systems is not uniform and various
methods may be used to measure a given analyte. The
results for a reference material analyzed by a variety of
methods will be less predictable and the estimate of
"true values" less precise. The studies must discern the
overall reliability of the methods and identify methods
which tend not to measure the analyte. Studies will be
used to establish procedures which are uniform for a given
measurement principal. The data from such studies require
statistical evaluation and at time sophisticated matrix
solutions. These statistical evaluations will be processed
on ADP.
b. Methods may be used which are not designated as reference
or equivalent methods. Methods for many analytes have not
had suitable evaluations and accuracy is not known.
Thus, studies will be made by QAO to provide data files
on BAT when such information can be obtained. Data files,
data systems such as Comnet. EMSL-Cincinnati , etc., will
be accessed through a Tektronix 4014 terminal.
c. Laboratories will be evaluated by performance audits and
system evaluations which will include methodology, calibration,
training, maintenance and other operations. Audit data and
production records will provide a measure of the effectiveness
of the quality control program.
4. Independent audits for determination of measurement accuracy
will be managed by QAO. The individuals performing audits may
be located at the Region V, QAO or in the various S&A district
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offices. The audit procedures will be prepared by QAO or if I
audits are performed by personnel other than QAO those procedures
will be approved by QAO.
State and local agencies will develop their audit procedures.
Conformance with Federal Rgulations and EPA Guidelines will be
determined by QAO. Audit procedures must be reviewed by the I
appropriate agency on an annual basis and revised as appropriate.
Revisions must be approved by QAO.
Each instrument will require an independent audit performed by a |
State agency, Region V or by contract. The frequency of audits is
to be based on requirements of regulations, EPA guidelines or _
Region V policy. I
Some audit results may be reported by ADP terminal as soon as ADP
is functional, to QAO for storage in suitable data files. These
audit reports would provide date, time, auditor, analyte, method,
instrument (reference method, equivalent non-equivalent), agency
name, site number, temperature, pressure, all pertinent technical
data and values observed. A written report to the agency and the
respective Region V media program manager will be made indicating
acceptability of performance and/or corrective action required
and expected time required to meet compliance.
The operating agency will acknowledge corrective action and reply
by indicating that corrective action was taken or would be completed
by a given date. Where corrective action can not be made with
existing equipment, intended action must be indicated. The QAO
will review the operating agency response for acceptability.
A re-audit will be scheduled by QAO and effectiveness of
corrective action verified. Verification will be made by an
appropriate QAO staff member or appropriate auditor and reported
to QAO.
The final audit report is written up and reported formally. The
time of reporting will conform to the QAO program plan requirements.
The recipient of the audit report is the operating agency with copies
sent to the respective media program manager.
Reports of unacceptable audits sent to the QAO will automatically
be flagged for the particular instrument. Data will be invalidated
or held in storage as invalid until corrective actions are completed.
This system will improve on the data analysis over the present system
because audits are not presently correlated with the data until after
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summaries have been prepared. Thus, it is necessary to go backwards
and delete invalid date at a later date. There has not been a
systematic method for correlating audits with site data.
Types of instrument audits which will be made are:
a. Ozone calibration audits. These are resource intensive since
a calibration system must be maintained with strict quality
control measures. The method of measurement must be by the
reference method. The audit requires transporting a primary
calibration or a transfer calibrator to a monitoring site.
Multi-level calibration checks are made which may require as
much as 3 to 4 hours operating time. These audits will be
performed by auditors located in the district offices and
verified by QAO, or performed by QAO.
Audit results for all systems in the Region are correlated to
estimate a "true value" to define accuracy of ozone measure-
ments in Region V.
Frequency of ozone audits and the acceptable limits are
defined in 40 CFR 53, Appendix A. State and local agencies
will be audited with a minimum number of audit frequencies
described in the Appendix A of the regulations. Greater
frequencies are encouraged to the limit of cost effectiveness.
Present auditing levels in Region V are greater than the
minimum required in proposed regulations. These levels of
audits are considered justified since they improve cost
effectiveness. Quicker turn around time on audit reports
and improved operations might suggest a lesser frequency, but
demonstration of the appropriate levels will result from the
evaluations established in this program.
b. Hi-Vol Sampler audits are resource intensive requiring travel
to monitoring sites, measurement of several flow rates and
evaluation of operations and equipment. Personnel who audit
the Hi-Vol Samplers are from the District Offices. Audit is
verified by the QAO. Frequency of audits are determined by
QAO based on regulations, EPA guidelines or Region V policy.
Hi-Vol Samplers are audited by Region V, State and local
agencies on a frequency which is greater than that required by
40 CFR 53, Appendix A. Acceptable limits applied in Region V
are tighter than required by Appendix A.
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Audit reports are transmitted to the QAO for verification.
A copy of the report will be provided to the Agency audited
and to the appropriate media program manager in Region V.
The report records temperature, pressure, unusual instrument
findings, site number, Agency name and two or more observed
flow rates using reference plates. Reference plates are
calibrated by equipment which has been referenced to the
highest standards available.
c. Calibration equipment: QAO will procure, operate and maintain
calibration equipment required for all measurement parameters.
Procedures, specifications, operation manuals, maintenance
manuals and spare parts lists will be compiled for use with
this equipment and made available for Regional, State and
local agency use/or information from the Central Reference
Files. List of vendors will be documented for ready reference
in order to expedite replacement of equipment. Calibrations
will be made on various instruments for measurement of critical
pollutants, particularly continuous monitors. QAO will maintain
quality control records on these instruments.
d. Audits on detector sensitivity for spectrometers, pH meter
accuracy, etc., will also be made on an instrument-by-instrument
basis.
8.7.2.2 Management of the On-Site System Evaluation of Total In-House,
Federal, State and Local Agency, Contractor, Grantee Monitoring
Program
The Quality Assurance Office has total responsibility for managing
the system evaluation program. A system evaluation is an on-site
inspection and review of the quality control program used for the
total measurement system for each specific monitoring program
conducted by a Federal, State or local agency. For convenience,
some items that each quality control plan must contain (discussed
elsewhere in this document) and which will be evaluated are repeated
below:
1. Organization and Responsibility - Is the quality control
program operational?
2. Sample Collection - Are written procedures available for sample
collection and are these followed as documented?
3. Sample Analysis - Are written analysis procedures available
and are procedures followed as written?
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4. Data Validation - Is a list of criteria for data validation
available and it it used?
5. Calibration - Are written calibration procedures available and
are procedures followed as written?
6. Performance Evaluations - Are control charts for performance
evaluations reviewed and corrections made when indicated?
7. Intralaboratory Tests - Are results from intralaboratory testing
reviewed and corrections made when indicated?
8. Preventive Maintenance - Is the preventive maintenance schedule
being followed as recommended in the QA plan?
The results of the system evaluation is documented by the QAO
for presenting a visual picture of the performance of the program
to see if the minimum requirements of the Region's Quality Assurance
Plan are being met. If not, deviations are identified and
recommendations made for corrections. If corrections are not
made, recommendations are made to the appropriate program director
for action (eg., withholding grant or contract funds, etc.).
Appendix 17 depicts how the system evaluation program will function.
A system evaluation will be conducted at all laboratories in
Region V funded by EPA engaged in the Clean Water or Clean Air Act,
the Safe Drinking Water Act, the Toxic Substance Control Act, and
other pertinent Acts. All parameters analyzed for, will be evaluated.
The minimum QC elements for these laboratories for several major
programs are listed in Appendix 18 and 19 and will be evaluated
for compliance with these minimum requirements. The minimum QC
elements for the above laboratories engaged in the Clean Air Act
monitoring activities are listed in EPA publications 600/9-76-005,
600/4-77-027a, and 600/4-77-127b, "Quality Assurance Handbooks
for Air Pollution Measurement Systems", and 40 CFR Part 58, Appendix
A and B. Laboratory evaluations will be based on compliance with
minimum requirements contained in these documents.
The on-site evaluation programs will be administerd as separate
operations. These will be evaluations of the:
a. State principal laboratories and offices (water and wastewater).
b. State principal laboratories and offices (air).
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c. Local laboratories analyzing public water supply samples.
d. Local air agency offices.
e. Contract laboratories.
This division of work is required because of the administrative
separation of the programs.
DATA PROCESSING
The term "data processing" is used to include handling, validation,
verification, transmission and storage, and reduction, including
software QC considerations as described below. Just as samples and
specimens can be destroyed, data can be lost, distorted, misinterpreted,
incorrectly transcribed, improperly transposed, overlooked, or subject
to other distortions, unless suitable QC procedures are used to protect
its integrity.
To obtain meaningful environmental data, the representative sample
must be delivered unchanged to the analyst who will develop the
needed data by performing the prescribed analysis. The completed
(i.e., calculated) results need verification calculations to eliminate
outliers or extraneous results and the conversion of acceptable results
to some final form for permanent recording of the analytical data in
meaningful exact terms. These results are then transferred to a data
storage facility for future interpretation and use. All quality
control plans must document the mechanism to deal with those requirements
listed in 9.1. 9.2 and 9.3. Those mechanisms shall be as stringent as
those specified below.
9.1 Data Handling Transmission and Storage
Measurements of the concentration of pollutants, either in the
ambient environment or in the emissions from stationary sources,
are assumed to be representative of the conditions existing at
the time of the sample collection. The extent to which this
assumption is valid depends on the sources of error and bias
inherent in the collection, handling, and analysis of the sample.
Besides the sampling and analytical error and bias, human error
may be introduced any time between sample collection and sample
reporting. Included among the human errors are such things as
failure of the operator/analyst to record pertinent information,
mistakes in reading an instrument, mistakes in calculating results,
and mistakes in transposing data from one record to another.
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Data handling systems involving the use of computers are susceptible
to keypunching errors and errors involving careless handling of
magnetic tapes and other storage media. Although it cannot be
completely avoided, human error can be minimized.
Data reporting techniques and error sources depend on the type of
sensor measurement system. Measurement sensors for pollutant
concentration may be classified by their sample collection principle
into two categories: (1) Integrated, and (2) Continuous. Pollutant
measurement systems may be either integrated or continuous, whereas
ambient measurement systems are normally always continuous.
In the integrated sample collection principle, a discrete sample
is collected in some medium and is normally sent to a laboratory
for analysis. The sampler, field operator and the laboratory
analyst can make errors in data handling.
In the continuous sample collection principle, an analytical sensor
produces a direct and continuous readout of the pollutant concentration
parameter. The readout may be a value punched or typed on paper
tape or recorded on magnetic tape. In addition, some continuous
measurements systems may also use telemetry to transmit data to a
data processing center. Both human and machine errors can occur
in data handling in this type of system.
a. Data errors in integrated sampling - For ambient monitoring,
the sampler or operator records information before and after
the sample collection period. For source emission testing,
the operator records information during the sample collection
period in addition to before and after it. Acceptance limits
should be set for data pertaining to flow rates, etc., and
the operator/analyst should invalidate or "flag" sampling
data when values fall outside these limits. Questionable
measurement results may indicate the need for calibration or
maintenance.
The analyst in the laboratory reads measurements from balances,
colorimeters, spectrophotometers, and other instruments; and
records the data on standard forms or in laboratory notebooks.
Each time values are recorded, there is a potential for incorrectly
entering results. Typical recording errors are transposition
of digits (e.g., 216 might be incorrectly entered as 126) and
incorrect decimal point location (e.g., 0.0635 michg be entered
as 0.635). These kinds of errors are difficult to detect.
The supervisors must continually stress the importance of
accuracy in recording results.
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Acceptance limits contained in the measurement method write-up
and those shown in the method activity matrix should be used
by the analyst to invalidate or "flag" analysis data when
values fall outside these limits. |
b. Data errors in continuous analyses - Continuous monitoring _
systems may involve either manual or automated data recording. I
Automated data recording may involve the use of a data logging m
device to record data on paper tape or magnetic tape at bench
or the remote sampling station, or the use of telemetry to I
transmit data on-line to a computer at a central facility. I
Manual reduction of pollutant concentration data from strip
charts can be a significant source of data errors. In addition I
to making those errors associated with recording data values
on record forms, the individual who reads the chart can also
err in determining the time average value. Usually the reader
estimates by inspection the average concentration. When the
temporal variability in concentration is large, it is difficult
to determine an average concentration. Two people reading
the same chart may yield results that vary considerably.
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Persons responsible for reducing data from strip charts should _
be given training. After a person is shown how to read a
chart, his/her results should be compared with those of an
experienced analyst. Only after he/she has demonstrated the
capability to obtain satisfactory results should a analyst be
assigned to a data reduction activity. |
Periodically the senior analyst or section chief should check _
strip charts read by each analyst.
Up to 10 percent of all data reported by each analyst is to
be checked by the Quality Assurance Coordinator for errors.
If an individual is making gross errors, additional training |
is to be provided.
Because manual chart reading is a tedious operation, a drop I
in productivity and an increase in errors might be expected
after a few hours. Ideally, and individual should be required
to spend only a portion of a day at this task.
The use of a data logging device to automate data handling
from a continuous sensor is not a strict guarantee against
data recording errors. Internal validity checks are necessary I
to avoid serious data recording errors. There are two sources
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of error between the sensor and the recording medium: (1) the
output signal from the sensor and (2) the errors in recording
by the data logger.
The primary concern about the sensor output is to ensure that
only the sensor analog signal and not electronic interferences
be converted to a digital readout. Internal validity checks
should be planned to "flag" spurious data resulting from
electronic interferences.
For a system involving the use of telemetry, it is also necessary
to include a validity check for data transmission.
Errors in computations - To minimize computational errors,
operators and analysts should follow closely the formulae,
calculation steps, and examples given for each method, using
the calculation instructions and forms provided in the method
write-up.
The senior analyst should check the computations of each analyst.
Up to 10% of all data reported computations are to be checked
by the QA Coordinator for errors.
Control charts - Procedures for reviewing data at the operational
as well as the managerial levels.are to be implemented by data
generators (lab and field). Review of measurement results
from control samples used during analysis, for example, can
indicate out-of-control conditions that would yield invalid
data from subsequent analyses, if the conditions are not
corrected immediately. At the managerial level, periodic review
of data can indicate trends or problems that need to be addressed
to maintain the desired level of precision and accuracy. One
common tool for statistical analysis of data at both the
operational and the managerial levels is the control chart.
The major steps in constructing the control chart were outlined
in Section 8.7.1.
The control chart provides a tool for identifying the systematic
variation (assignable cause) from the system indeterminate
variation (random). This technique displays data in a form
that graphically compares the variability of all test results
with the average or expected variability of small groups of
data.
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The steps to consider in the application of control charts I
are the following:
1. Select critical characteristics in the measurement system to I
audit.
2. If audit (reference) standards are used, obtain the necessary I
materials.
3. Select the data quality objective to audit:
a. Precision - A measure of mutual agreement among
individual measurements of the same property, usually
under prescribed similar conditions. I
b. Accuracy - The difference between an average value
and the true value when the latter is known or assumed.
4. Choose the audit size and frequency:
a. Size - i.e., for air analysis, the analysts will often be I
dealing with samples of 2, which will form most subgroups.
b. Frequency of subgroup sampling - Changes are detected more
rapidly as the sampling frequency is increased. Audit
rates of 7-10 percent are recommended for many
characteristics shown in the method activity matrices.
5. Set control limits, Control limits (CL) are to be set at
2 times the standard deviation for P
6. The control charts are to be maintained either by the
operator/analyst or the supervisor. The control chart
should be kept up to date. The QA coordinator is to
review the charts on some established frequency. After
establishing 15 to 20 data points, the control limits
should be reestablished on the basis of these data. If
the new control limits are narrower than those recommended,
the former is to be used. After this initial calculation,
control limits should be recalculated every 3 to 6 months,
or whenever significant data trends or shifts become
obvious.
The control chart is actually a graphical presentation of
quality control effectiveness. If the procedure is
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"in control", the results will almost always fall within
the established control limits. Further, the chart will
disclose trends and cycles from assignable causes that
can be corrected promptly.
Report Forms - The analytical information reported should
include the measured parameters; the details of the analyses
such as burette readings, absorbance, wavelength, normalities
of reagents, correction factors, blanks; and the reported
data values. To reduce errors in manipulation of numbers
a general rule is to reduce handling and transposition of
date to an absolute mini num. Ideally, a report form includes
preliminary information about the sample and its analysis,
and the same form is used for the final reporting form for
entering of data into a computer. However, if such a set-up
is not available the protocol below is to be used to record
finali zed data.
1. Loose Sheets - Reporting of data onto loose or ring-binder
forms is a means of recording data that allows easy addition
of new sheets, removal of older data, or collection of
specific data segments. However, the easy facility for
addition or removal also permits loss or misplacement of
sheets, mixups in date sequence, and ultimately questionable
status of the data for formal display or presentation as
courtroom evidence. Loose sheets are not encouraged.
2. Bound Books - The use of bound books is an improvement
in data recording that tends to result in a chronological
sequence of data insertion. Modification beyond a simple
lined book improves its effectiveness with little additional
effort. Numbering of pages encourages use of data in
sequence and also aids in referencing data through a
table of contents ordered according to time, type of
analysis, kind of sample, and identity of analyst.
Validation can be easily accomplished by requiring the
analyst to date and sign each analysis on the day completed.
This validation can be strengthened further by providing
space for the laboratory supervisor to witness the date
and the completion of the analyses.
A further development of the bound notebook is the
commerically available version designed for research-type
work. These notebooks are preprinted with book and page
numbers, and spaces for title of project, project number,
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analyst signature, witness signature, and dates. Each
report sheet has a detachable duplicate sheet that allows
up-to-date review by management without disruption of the
notebook in the laboratory.
Bound notebooks can and should be used in routine
analytical laboratories. The need for repeated information
on sampling and analyses can be answered by use of preprinted
pages in the bound notebook.
Preprinted Report Forms - Most field laboratories and
installations repetitively analyzing fixed parameters develop
their own system of compiling laboratory data that may include
bound notebooks, but a means of forwarding data is also required.
Usually, laboratories design forms to fit a related group of
analyses or to report a single type of analysis for a series
of samples. As much information as possible is preprinted to
simplify use of the form. With loose-sheet, multicopy forms
(using carbon or FCR paper) information can be forwarded on
the desired schedule while also allowing retention of data in
the laboratory. Still, the most common means for recording
data in rough form are internal bench sheets or bound books.
The bench sheet or book never leaves the laboratory but serves
as the source of information for transfer of data to appropriate
report forms.
In most instances the supervisor and anlayst wish to look at
the data from a sampling point or station in relation to other
sampling points or stations on or in a particular AQCR, river
or lake. This review of data by the supervisor prior to
release is a very important part of the QC program of the
laboratory; however, such reviews are not easily accomplished
with bench sheets. For review purposes, a summary sheet can
be prepared that displays a related group of analyses from a
number of stations. The form should contain space for all of
the information necessary for reporting data, the completed
form can also be used to complete the data forms forwarded to
the computer storage and retrieval system.
The forms used to report to storage systems provide spaces
for identification of the sampling point, the parameter code,
the type of analysis used, the reporting terminology. Failure
to provide the correct information can result in rejection of
the data, or insertion of the data into incorrect parameter
fields. As sample analyses are completed, the data values
are usually reported in floating decimal form along with the
code numbers for identifying the parameter data fields and
the sampling point data fields.
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4. Plastic-Coated Labels and Forms - A recent addition to good
sample handling and data management is the availability of
plastic-coated (blank or preprinted) labels, report forms,
and bound report books. These materials are waterproof, do
not disintegrate when wet or handled, can be written on while
wet, and retain pencil or waterproof ink markings though
handled when wet.
5. Digital Readout - Instrumental analyses, including automated,
wet-chemistry instruments such as the Technicon Auto Analyzer,
the atomic absorption spectrophotometer, the pH meter, and the
selective electrode meter, provide digital readout of concen-
trations, which can be recorded directly onto report sheets
without further calculation. Programmed calculators can be
used to construct best-fit curves, to perform regression
analyses, and to perform a series of calculations leading to
final reported values.
6. Keypunch Cards and Paper Tape - Because much of the analytical
data generated in laboratories is first recorded on bench
sheets, then transferred to data report forms, keypunched,
and manipulated on small terminal computers (or manipulated
and stored in a larger data storage system), there is a danger
of transfer error that increases with each data copy. The
analyst can reduce this error by recording data directly from
bench sheets onto punch cards that can be retained or forwarded
immediately to the data storage system. Small hand-operated
keypunch machines are available.
7. Automated Laboratory Systems - The use of digital readout,
keypunch cards, and paper tape have been overshadowed by the
development of customized, fully automated online computer
systems that make measurements, calculate results, perform
qulaity control, and report analytical data simultaneously
from a full range of laboratory instruments. Such systems
can contain the following functions:
a. Manual or automatic sampling and testing of a series of
samples, standards, replicates and check samples.
b. Detection of the measurement signals from the series of samples,
c. Conversion of signals to concentrations, generation of a
standard curve, and calculation of sample values in final
units.
d. Calculation of the deviation and recovery values of the
results and indication of acceptance or nonacceptance
based on limits established by the analyst.
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e. Provision of the output in a form designated by the analyst:
dial, paper recording chart, digital readout, cathode ray
tube, or printed report form.
The degree of hands-on operation required in the system is specified
by the analyst.
If an automated system is properly designed and operated, most
calculation and transposition errors are avoided and the proper
level of quality control is automatically exerted.
9.2 Data Validation and Verification
Data validation is the process whereby data are filtered and
accepted or rejected based on a set of criteria. This involves
a critical review of a body of data in order to isolate and locate
spurious values. It may involve only a cursory scan to detect
extreme values or a detailed evaluation requiring the use of a
computer. In either situation, when a spurious value is located,
it is not immediately rejected. Each questionable value must be
checked for validity. Records of values that are either judged
invalid or are otherwise suspicious should be maintained. These
records are, among other things, a useful source of information for
judging data quality. Validation methods can be manual or by
computerized techniques.
a. Manual - Both the analyst and the laboratory supervisor should
inspect integrated environmental quality monitoring data.
At regular intervals, daily or weekly, results should be
scanned for questionable values. This type of validation is
most sensitive to extreme values, i.e., either unusually high
or low concentrations. These are sometimes called outliers.
The criteria for determining an extreme value are derived from
prior data obtained at the particular sampling site (or a similar
site if no previous data are available for a site). The data used
to determine extremes may be the minimum and maximum concentrations'
for all prior data from a site. The decision criteria might
also be based on minimum and maximum for each season, each
month, or each day.
An audit level of 7-10 percent should be established for
checking data, i.e., checking 7-10 out of every 100 values.
b. Computerized Techniques - A computer can be used not only to
store and retrieve data but also to validate data. Any
system for checking extreme values in manaul techniques also
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apply here. The criteria for extreme values can be refined
to be specific for individual hours during the day. For
example, with this procedure, an hourly average concentration
for carbon monoxide of 15 ppm may not be considered an extreme
value for 8:00 a.m. but could be tagged as questionable if it
appeared at 2:00 am.
Another indication of possible spurious data is a large difference
in concentrations reported for two successive time intervals.
The difference in concentrations, which might be considered
excessive, may vary from one time to another for the same
pollutant. Ideally this difference in concentration is
determined through a statistical analysis of historical data.
For example, it may be determined that a difference of 0.05
ppm in the S02 concentration for successive hourly averages
occurs rarely (less than 5 percent of the time). But at the
same station the hourly average CO concentration may change
by as much as 10 ppm. The criteria for what constitutes an
excessive, change may also be linked to time of day and pollutant
relationships, e.g., high concentrations of S02 and 03 can
not co-exist and these data should be considered suspect.
Criteria for Determining Acceptability of Data - Reading strip
charts is a tedious job subject to varying degrees of error.
A procedure for maintaining a desirable quality for data
manually reduced from strip charts is important. One procedure
for checking the validity of the data reduced by a analyst is
to have another analyst or the supervisor check the data.
Because the values have been taken from the strip chart by
visual inspection, some difference in the values derived by
two individuals can be expected. When the difference exceeds a
specified amount and the initial areadi ng has been determined
to be incorrect, an error should be noted. If the number of
errors exceeds a predetermined number, all data for the strip
chart are rejected and the chart is read again by a technician
other than the one who initially read the chart. The question
of how many values to check can be answered by applying one
of two techniques.
1. Application of Acceptance Sampling Techniques - Acceptance
sampling can be applied to data validation to determine the
number of data items (individual values on a strip chart)
that need to be checked to determine with a given probability
that all the data items are acceptable. The supervisor
wants to know, without checking every data value, if a
defined error level has been exceeded. From each strip
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chart with N data values, the supervisor can randomly I
inspect n data values. If the number of erroneous values
is less than or equal to c, the rejection criteria, the
values for the strip chart are accepted. If the number
of errors is greater than c, the values for the strip
chart are rejected, and another analyst is asked to read _
the chart.
2. Sequential Analysis Test Procedure - The typical approach
used in performing a statistical test of hypothesis
requires the collection of a sampTe of a fixed size. A
statistic is then computed from the sample data and compared
with some critical values for that statistic. A decision _
is then made to accept the hypothesis (H0) or to accept I
some a-1 tentative hypothesis (HI). With such a procedure
it is necessary to collect the specified sample of observations
regardless of the results that may be obtained from the
first few observations. I
Sequential analysis requires that a decision be made .
after each observation or group of observations. This I
procedure has the advantage that, on the average, a decision
can be reached with fewer observations than a fixed sample
size requi res.
Data Validations Procedures and Criteria for the Agency's
National Aerometric Data Bank (NADB)
The NADB is a computer storage and retrieval system for
aerometric data collected by Federal, State and local air agencies.
40 CFR Part 58.35 specifies the NAMS data submittal requirements I
to NADB which are 1 si ted below:
The requirements of this section apply only to those
stations designated as NAMS by the network description
required by §58.30.
The State shall report quarterly to the Administration «
(through the appropriate Regional Office) all ambient air
quality data and information specified by AEROS Users
Manual (EPA-450/2-76029, OAQPS No. 1.2-039) to be coded |
into the SAROAD Air Quality Data forms. Such air quality
data and information must be submitted on either paper _
forms, punched cards, or magnetic tape in the format of I
the SAROAD Air Quality Data forms.
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c. The quarterly reporting periods are January 1-March 31,
April 1-June 30, July 1-September 30, and October 1-December 31,
The quarterly report must:
1. Be submitted within 90 days of the end of each reporting
period, and
2. Contain all data and information gathered during the
reporting period.
d. The first quarterly report will be due on or before
June 30, 1981, for data collected during the first quarter
of 1981.
e. Air quality data submitted in the quarterly report must
have been edited and validated so that such data are
ready to be entered into the SAROAD data files. Procedures
for editing and validating data are described in AEROA
Users Manual (EPA-450/276-029, OAQPS No. 1.2-039).
f. This section does not permit a State to exempt those
SLAMS which are also designated as NAMS from all of any of the
reporting requirements applicable to SLAMS in §58.26.
Highlights from the above documents for data validation are
described below:
1. Screening Criteria - In order to draw correct conclusions
from the data, validity checks are built into the data
handling system. The data must meet predetermined standards
with respect to representativeness, instrument averaging
time, duration of sampling, and comparability before
they are incorporated into NADB. A discussion of each
criterion follows:
a. Representativeness - Data from each monitoring site
should characterize ambient levels in an area or
neighborhood. For example, a daily average of carbon
monoxide calculated from values collected only during
the morning rush hour would hardly reflect the true
daily averages. The data must be relatively complete
over the time interval of interest (for example, day,
season, or year) so that such biases can be avoided.
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b. Instrument Averaging Time - The data must represent a I
sample interval of 1 hour or more. Thus, no more
than 24 values per day per pollutant are stored.
Data for intervals of less than 1 hour are converted
to hourly averages before storage.
c. Duration - The data must be collected over a time period I
of no less than 3 consecutive months so that at least
quarterly summary statistics can be calculated.
d. Comparability - Aeromatic data must be maintained in
consistent units to permit data submitted by various
agencies to be combined into nationwide summaries and _
evaluation reports. The data must have been acquired I
by application of standard methodologies. "
These four criteria are pertinent to developing meaningful
information from the data collected from any monitoring network^
Criteria for Completeness. The raw data entering the NADB M
are checked for completeness (representativenesss). With
continuous measurement, the criterion for completeness is
that at least 75 percent of the total possible number of
observations be present. Figure 9.2 presents the number
of observations required by the NADB before summary results I
are calculated.
The data within the NADB resulting from intermittent sampling I
are summarized only if there are at least five samples
per quarter. An additional stipulation is that if a
month contains no samples each of the other 2 months in I
the quarter must contain at least 2 samples. Any other
distribution of samples over the quarter is acceptable.
This is a minimum criterion based on a random biweekly
sampling schedule. A more stringent criterion should be
applied when the sampling schedule is every third or
sixth day.
Criteria for Accuracy and Precision - Accuracy and precision
data reported with aerometric data are not used to validate
data before entry into NADB but are used to interpret the
data. |
Criteria for Handling Data Values below Minimum Detectable
Limits - Concentrations below the limit of detection of I
the instruments employed result in the problem of determining *
how to report such values so that summary statistics can
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Continuous measurement criteria for completeness
I
Time interval
Minimum number of observations
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3-hour running average
8-hour running average
24-hour
Monthly
Quarterly
Yearly
3 consecutive hourly observations
6 hourly observations
18 hourly observations
21 daily averages
3 consecutive monthly averages
9 monthly averages with at least
two monthly averages per quarter
Figure 9.2 Criteria for completeness for continuous ambient
air monitors for NADB
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91
be calculated. The choice of data values is complicated by
the fact that zero, the most likely value to be supplied,
cannot be used, especially if geometric parameters are to
be calculated.
This problem is handled by inserting a constant, approxi-
mately equal to one-half the minimum detectable limit,
for each method and analysis technique. This value was
chosen after examining the lower end of the cumulative
distributions for the various pollutants. Seldom did the
log-normal distribution (the distribution most often
applied to air pollution data) accurately describe this
portion of the data. This may be due in part to the
existence of a background level for each pollutant. Use
of the midpoint between zero and the detectable limit as
the substitute value for concentration levels below the
detection threshold seems reasonable. In order to permit
consistency from year to year, one minimum detectable
value is used for each pollutant even if the minimum
detectable limit is changed, unless there is a change by
an order of magnitude. Figure 9.2.1 provides an example
of the current minimum detectable limits as used by the
NADB for each pollutant and the value to be inserted for
each value below the minimum detectable limit. These
minimum detectable limits are reviewed periodically and
changed as required. Each laboratory should determine
its own set of minimum detectable limits, based on its
own analytical techniques and instruments, to generate
pollutant information.
One additional point should be mentioned concerning the
use of substituted values for values below the threshold
of the method. When more than 25 percent of the measured
levels are below the minimum detectable quantity, no
statistics are computed from the data. This contraint guards
against the possibility of biasing the computed statistics.
Furthermore, at least 50 percent of the measurements in a
set of data must be above the minimum detectable concentration
before a frequency distribution of the values can be
prepared.
5. Criteria for Handling Data with Negative Values - For the
purpose of generating true pollutant values, negative
pollutant concentrations imply that there is not enough
of the pollutant present for the instrument to detect
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above the noise limit specified for the instrument. |
When negative values occur, they should be regarded as
being below the detection limit for the method and treated »
in the same manner, i.e., assigned a value one-half the I
minimum detectable limit.
9.3 Data Reduction (Including Software QC Considerations)
The effectiveness of the quality assurance program will be I
determined by monitoring improvements in the reliability
of reported QC data. On a regular basis, the QAO will critically
evaluate all reported QC data for each reporting unit. It is I
believed that this approach will provide a data base to more
accurately evaluate and improve measurement performance. The QAO
will use a number of statistical techniques and ADP to measure I
performance, which are briefly described below. These techniques B
have been reviewed extensively elsewhere in this document.
a. Summary Statistics - Summary statistics such as the mean |
and the standard deviation will be used to simplify the
presentation of data and at the same time to summarize essential _
characteristics.
b. Frequency distributions - Frequency distributions such as
normal and log-normal distributions will be used to present
relatively large data sets, such as the daily concentrations |
of suspended particulates in ambient air over a long period
of time, i.e., six months.
c. Estimation and testing procedures - Statistical estimation *
and testing procedures will be used to make inferences
concerning the conceptual population of measurements made
under the same conditions based on a small sample of data. I
An example would be the estimation of the average pH of a
large number (population) of filters based on a sample (lot) M
of pH readings for seven filters.
d. Outliers - Outliers, i.e., unusally large or small values,
are identified by appropriate statistical tests for outliers.
These statistical tests are useful, for example, in identifying
gross errors in data handling procedures.
e. Audit data - Statistical methods for treating performance |
audit data and for presenting the results in terms of bias
and precision will be used.
f. Replication, repeatability, and reproducibility tests - The
identification of sources of measurement error within and
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among laboratories is one of the important functions of the
Quality Assurance Office. Statistical methods will be used
to identify these measurement errors.
Quality control audit data from up to 50 laboratories using
several hundred different methods to monitor several hundred
different contaminants must be monitored on a continuing basis.
This workload requires extensive use of computer technology and
considerable skill in interpreting the results. The statistical
software package that has been identified in the description of
needs, once developed and implemented will be able to handle this
large volume of data and generate reports that describe data
quality in non-technical language for the data users. Reports
will also be produced for laboratory and field personnel describing
their performance relative to that of other groups using similar
measurement procedures. It is intended that these reports will
generally be in a graphical format and include a listing of all
supporting results.
The QAO data files will be protected in the ADP system per the
file protection protocol for the ADP system. Files will not be
accessible to other offices. Programs will be stored as "Declared
Files". The original documentation of the software programs will
be placed in the permanent files of the QAO in case there is ever
a need to refer back to this documentation. Updated print-outs
will also be maintained on all file data in case the data is lost
due to some hardware malfunction of the ADP system.
10. CORRECTIVE ACTIONS
Corrective actions are of two types:
a. On the spot or immediate - This is the process of correcting
malfunctioning equipment.
In a quality assurance program, one of the most effective means
of preventing trouble is to respond immediately to reports from
the operator of suspicious data or equipment malfunctions. Application
of proper corrective actions at this point can reduce or prevent
the collection of poor quality data. Established procedures for
corrective actions are available in the methods if the performance
limits are found to be exceeded (either through direct observation
of the parameter or through review of control charts). Specific
control procedures, calibration, pre-sampling or pre-analysis
operational checks, etc., are designed to detect instances in
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which corrective action is necessary. A check-list for logical
alternatives for tracing the source of a sampling or analytical
error is provided to the operator. Trouble shooting guides
for operators (field technicians or lab analysts) are generally |
found in instrument manufacturer's manuals. On-the-spot
corrective actions routinely made by field technicians or lab _
analysts should be documented as normal operating procedures, I
and no specific documentation other than notations in operations
logbooks need to be made. However, logbooks are to be made
available to QAO for review during any audit or on-site
system evaluation. J
Long-term Corrective Action - The purpose of long-term corrective _
action is to identify and eliminate causes of nonconformance or I
noncompliance with Agency QA requirements, Hopefully, they
will be eliminated permanently. To improve data quality to
an acceptable level and to maintain data quality at an acceptable
level, it is necessary that the quality assurance system be I
sensitive and timely in detecting out-of-control or unsatisfactory
conditions. It is equally important that, once the conditions of M
unacceptable data quality are indicated, a systematic and timely
mechanism is established to assure that the condition is reported
to those who can correct it and that a positive loop mechanism
is established to assure that appropriate corrective action I
has been taken. A system of reporting deficiencies and I
verifying corrective actions identified during the audit and
on-site sytem evaluation process has been identified earlier m
in this document and will not be repeated here. g
1. Closed-loop Corrective Action System for Major Problems -
Experience in Region V has been that most problems will I
not disappear until positive action has been taken by
management. The significant characteristic of any good
management system is the step that closes the loopthe
determination to make a change if the system demands it |
(this is mandated by the Agency's QC requirements and QA
regulations).
The following discussion outlines the considerations and procedures
necessary to understand and implement an effective closed-loop
corrective action system for major problems. Effective
corrective action occurs when many individuals and media I
programs cooperate in a well planned program. There are
several essential steps that must be taken to plan and implement
a corrective action program that achieves significant results. I
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Corrective actions should be a continual part of the laboratory
system for quality, and they should be formally documented.
Corrective action is not complete until it is demonstrated that
the action has effectively and permanently corrected the problem.
Diligent follow-up is probably the most important requirement of
a successful corrective action system.
Figure 10.1 illustrates the sequence of activities involved
in operating a closed-loop corrective action system.
10.1 QA Management
Sections 1 and 8.7.2 describes the management responsibility
for Region V's Quality Assurance Program. Feedback channels
are identified for keeping informed of the performance of all
monitoring systems in Region V funded by EPA. Procedures are
also identified to monitor the performance of the monitoring
systems. Elements of the program have been developed from the
QAO Functional Statement, Agency Regulations and requirements
which serve as the foundation of Region V's policy statement,
have been approved by the Regional Administration, making this
program binding on the Region. Goals have been identified (including
resources) to accomplish the objectives of this program.
10.2 QC Management
Each monitoring activity shall document and implement a quality
assurance policy approved by management to assure that sufficient
quality control activities are maintained to assure data
credibility for each monitoring project. Each monitoring project
shall designate a Quality Assurance/control coordinator (preferably
full-time) to be responsible for the environmental QC program,
coordinators can be appointed for specific monitoring activities,
i.e., Air coordinator, water coordinator.
a. Qualifications
1. The coordinator should have as a minimum a bachelor's
degree in physical science, chemistry, biology or microbiology,
with at least five years of experience in his respective
discipline. In addition, the coordinator must have
actively worked in a environmental quality laboratory
for at least two years. Experience in statistical quality
control techniques and/or academic courses in mathematics
and statistics is also highly desirable.
2. The coordinator maintains close liaison with the
appropriate EPA Regional Analytical Quality Assurance
Coordinator, and is responsible for the overall quality
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assurance program in his laboratory. The coordinator
should report to the appropriate level: It is highly
desirable that this function not be subordinate to an
individual responsible for direct conduct of sampling or
analyses. This arrangement is workable, however, if the
individual responsible for sampling and analyses maintains
an objective viewpoint. While the overall program workload
will determine whether this position is a full-time or
part-time responsibility, it should, in most cases be
full-time.
b. Duties and Responsibilities
The coordinator is responsible for developing and implementing
an inter-and-intralaboratory quality control program. Specific
duties include, but are not necessarily limited to:
1. Participating in the overall quality control plan.
This includes all elements of the sampling and analytical
programs. The coordinator carries out this activity
within EPA quality control and methodology guidelines.
Other recommended and accepted procedures can be used to
supplement these guidelines.
2. Administering the inter!aboratory quality control
program as a continuing in-house activity to ensure the
integrity and validity of analytical data.
3. Measuring the precision and/or accuracy of analytical
results. Providing on-line quality control of samples,
i.e., reference samples, duplicates, control charts,
spiked, and audit samples.
4. Providing a permanent record of instrument, and analyst
performance as a basis for evaluating data.
5. Identifying training needs and technical methodology
gaps.
6. Upgrading the overall quality of laboratory performance
by recommending procedural and personnel changes, as required,
to ensure the validity and integrity of the data.
7. Coordinating the inter-and-intralaboratory quality control
program with the QAO, Region V, and other governmental and
commercial laboratories. This involves participating in
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round-robin methodology studies, providing quality control
check samples, and performance of check samples to requesting
laboratories.
8. Evaluating and discussing the results of activities
outlined in Paragraphs 1 through 7 with the appropriate
individuals involved. When an analysis is out of control
or a discrepancy is noted, the coordinator should be
notified and appropriate corrective action should be
taken.
c. Competence of Personnel
The coordinator should develop a training program to
ensure a minimal level of proficiency. He must recognize
variations in ability and provide training to ensure that
professional skills are appropriate to the task. Training
programs should be administered in order to develop that
level of competence which is necessary to carry out assigned
functions. Moreover, these programs should be carried out in
full cooperation with EPA Region V, Quality Assurance Office.
d. Basic facility and Equipment Requirements
The coordinator should establish basic requirements
(equipment, proper facilities, etc.) for operating an
environmental laboratory. These requirements should not be
included as part of the quality assurance budget. Laboratory
facilities should provide an environment free from atmospheric
contaminant levels which can affect the desired analyses.
The laboratory should be clean, air conditioned and/or heated,
and have a well lighted work area. Safety features and
other facilities consistent with opeational requirements
should be provided.
e. Initial On-Site Laboratory Evaluation
The coordinator will implement his planned quality assurance
program with an initial on-site laboratory evaluation.
Subsequent performance of analysis on audit samples and
participation in split sample program with the EPA regional
office should also be required.
11. DATA QUALITY ASSESSMENT
The assessment of data quality is the end result in a comprehensive
QC/QA program. Data quality assessment has four basic components:
1) accuracy, 2) precision, 3) completeness, and 4) representativeness.
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Each of these items is quantifiable and when suitably combined can
produce a numerical coefficient which is numerically proportional to
data quality.
A complete assessment of data quality, in terms of the four
components, is not possible at this time. However, this is the
primary goal of this QA effort. Air data is more advanced that
water and wastewater data at this time for such a comprehensive
assessment of data quality. However, with the implementation of
this plan during FY 80, a numerical assessment will be factored
into the FY 81 QA program plan activity. The primary key in this
activity is to get all quality control programs developed, approved
and implemented.
The four basic components of data quality assessment have been
elaborated on in great detail and their requirements are listed
elsewhere in this document, but will be summarized below.
11.1 /CCUR&Y ASSESSMENT
The QA Plan shall require that the accuracy of environmental
data be determined and reported provided that certified
reference materials are available or that measurements can
be traceable to a national standard.
11.2 PRECISION ASSESSMENT
The Region V QA Plan requires that the precision of
environmental data be determined on a routine basis and
reported to the suitable management authority as spelled out
in the QA and QC Management Section of this document (11.1 -
11.2).
11.3 COMPLETENESS ASSESSMENT
The Region V QA Plan requires that the completeness of
environmental data be assessed on a routine basis and reported
to the suitable management authority based on approved methodology.
Where the method is unapproved an alternate test procedure
approved by the Regional Administrator, shall be used. In
certain specific cases where methodology does not exist, the
QAO will request EMSL to specify a methodology for the Agency's
use.
11.4 REPRESENTATIVENESS ASSESSMENT
The Region V QA Plan requires that the representativeness of
environmental data be assessed on a routine basis and reported
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to the suitable management authority using approved method-
ology. Where the method is unapproved, the same protocol
specified in 11.3 is to be followed.
11.5 OVERALL DATA QUALITY ASSESSMENT
Overall data quality assessments are to be included with
each data report for water and wastewater at the start of FY
81. The overall data quality assessment for air data is
presently being reported.
12. DATA QUALITY REPORTS (QC AND QA)
The following types of QC, QA reports are to be prepared by each
monitoring group. These reports serve as a indicator of the monitoring
group's progress in implementing its Quality Assurance Program, which
monitor the various subunits1 performance of quality control procedures
and achievement of quality assurance goals.
1. Analytical reports. To maintain the required flow of QA and QC
information within a monitoring group, individual analysts, operators
and laboratories need to prepare QC reports on their monitoring-
and measurement activities. These reports are forwarded to the
QA coordinator, who then writes a QA report for the entire laboratory
organization.
2. Field Location reports. QD data for remote monitoring sites
must be developed and transmitted, either individually or grouped
by location (i.e., sectional or regional), to the QA coordinator.
3. Instrument inspection, calibration and maintenance reports. How
the instruments used in monitoring or measurement procedures are
inspected and maintained should be explained in a report to the
QA coordinator.
4. Reference materials and standards reports. The reference materials
used and standards followed must be stated. These reports should
cover not only, for example, the purity of chemical reagents,
but biological materials (such as a discussion of the availability
of a particular plant needed in experiments) as well.
5. Training reports (personnel). Who was given quality assurance
and/or quality control training? Did this training take place
in-house? How much did this training cost? The training reports
will answer these questions.
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6. Certification reports. These reports will be generated only
for the public water supply laboratory certification program.
The procedures for performance evaluation and certification of
both laboratories and personnel will be detailed in these reports.
7. Quality assurance reports. Reports detailing the unit's quality
control and quality assurance activities should be published on
a quarterly basis.
Distribution of and follow-up to these reports for corrective action
will be the same as that described for all other types of reports
described elsewhere in,this document.
13. CHAIN OF CUSTODY
The following procedures have been used successfully, and are
presented as suggested procedures insofar as they fulfill the legal
requirements of the appropriate State legal authority.
a. Procedures
Quality assurance should be stressed during all compliance
monitoring and when reviewing self-monitoring programs, no matter
what the reason for the spot check or inspection. Successful
implementation of a compliance monitroing program depends heavily
on the capability to produce valid data, and on clearly demonstrating
such validity. No other environmental monitoring area requires
more rigorous adherence to validated methodology and quality
control measures.
It is imperative that laboratories and field operations involved
in collecting primary evidence prepare written procedures. These
procedures should be used whenever evidence samples are collected,
transferred, stored, analyzed, or destroyed. A primary objective of
these procedures is to create an accurate written record which can be
used to trace possession of the sample from the time it is collected
through its introduction into evidence.
b. Preparing Samples
The evidence-gathering portion of a survey is characterized by an
absolute minimum number of samples required to give a fair
representation of the effluent or water body sampled. The quantity
and location of samples are determined before the survey.
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Prepare chain-of-custody record tags before actual field survey
work. Ensure tags contain all possible information to minimize
clerical work by field personnel. Also write the source of each
sample on the container before starting any field survey work.
Field logsheets used to document field procedures and chain-of-
custody, and to identify samples, should be pre-filled in to the
extent practicable to reduce repetitive clerical field entries.
The sampler or project leader should maintain custody during
sampling, using the logbook. Any information from previous
studies should be copied (or removed) and filed before the logbook
is returned to the field.
Follow explicit chain-of-custody procedures to maintain the
documentation necessary to trace sample possession from the time
the sample is taken until the evidence is introduced into court.
A sample is in your custody if:
o It is in your physical possession; or
o It is in your view, after being in your physical possession; or
o It was in your physical possession and you locked it in a
tamper-proof container or storage area.
All survey participants should receive a copy of the study plan
and should be familiar with its contents before the survey begins.
A pre-survey briefing should be held to inform all participants
of the survey objectives, sample locations and chain-of-custody
procedures. After all chain-of-custody samples are collected, a
debriefing should be held in the field to verify that chain-of-custody
procedures have been followed, and to determine if additional
evidence samples are required.
c. Collecting Samples
1. Ensure that the smallest possible number of people handle
the sample.
2. Obtain stream and effluent samples using standard field
sampling techniques. When using sampling equipment, assume
it is in the custody of the source being sampled.
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3. Attach chain-of-custody record tag to the sample container
when the complete sample is collected. Ensure the container
has the following information: sample number, time taken,
date taken, source of sample (include type of sample and
name of firm), preservative, analyses required, name of
person taking sample, and witnesses. The front side of the
card (which has been prefilled) is signed, timed, and dated
by the person doing the sampling. Tags must be legible and
filled out in ballpoint (water-proof ink). Secure individual
sample containers or group of sample containers using a tamper-
proof seal.
4. Take blank samples. Include one sample container without
preservative, and containers with preservatives. The laboratory
will analyze these contents to verify that no containers are
contaminated.
5. Maintain an up-to-date Field Data Record Logbook. Record
field measurements and other pertinent information necessary
to refresh the sampler's memory if, later on, he takes the
stand to testify regarding his actions during the evidence-
gathering activity. Maintain a separate set of field notebooks
for each survey; store them in a safe place where they can
be protected and accounted for at all times. Standard formats
have been established to minimize field entries; these include
the date, time, survey, type of sample taken, volume of each
sample, type of analysis, sample number, preservatives,
sample location and field measurements (temperature, conductivity,
DO, pH, flow), and any other pertinent information or observations.
The field sampler signs the entries. The survey coordinator
is usually responsible for preparing and conserving the field
logbook during the survey. Once the survey Is complete,
field logs will be retained by the survey coordinator or his
designated representative, as a part of the permanent record.
6. The field sampler is responsible for the care and custody
of the collected samples until they are properly dispatched
to the receiving laboratory, or turned over to an assigned
custodian. The field sampler should verify that each container
is in his physical possession or in his sight at all times,
or is locked so that no one can tamper with it.
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7. Colored slides or photographs are often taken to show the
outfall sample location and any visible water pollution.
Written documentation on the back of the photo should include
the photographer's signature, and the time, date, and site
location. These photographs can be used as evidence, and
are handled by chain-of-custody procedures to prevent alteration.
d. Transfer of Custody and Shipment
1. When transfer!ng the possession of samples, the transferree
signs, dates, and times the reverse side of the chain-of-
custody record tag or record. Custody tranfers, if made to
a sample custodian in the field, are made for individual
samples. The chain-of-custody tag or card must be dated and
signed by the second person who takes custody. If a third
person takes custody, he must follow the same procedure. An
additional chain-of-custody tag or card is completed by
persons who thereafter, take custody. It is apparent, from
this chain, that the number of custodians should be minimal.
Additional tags or cards should be numbered consecutively.
2. If a custodian has not been assigned, the field custodian
or field sampler is usually responsible for properly packaging
and dispatching samples to the proper laboratory for analysis.
In that case, the "Dispatch of Sample" portion of the chain-
of-custody record tag or card should be properly filled out,
dated, and signed.
3. Ensure that samples are properly packed in shipping containers
(for example, ice chests) to avoid breakage. Ensure that shipping
containers are padlocked for shipment to the receiving laboratory.
4. Include a "Sample Transmittal Sheet" with all packages.
The original, and one copy generally accompany the shipment.
Mail copies directly to the laboratory, to data management
personnel, and to any other responsible agent. The survey
coordinator usually retains one copy.
5. If the package is sent by mail, ensure that it is registered
with return receipt requested. If package is hand-delivered,
record delivery in the logbook. Send receipts from post
offices and bills of lading to the laboratory custodians for
retention as part of the permanent chain-of-custody documentation.
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6. When samples are delivered to the laboratory, and appropriate
personnel are not there to receive them, samples should be
locked in a secure, tamper-proof area. The same person must
unlock the samples and deliver custody to the appropriate
custodian.
LABORATORY CUSTODY PROCEDURES
The following procedures are to be used by Region V monitoring
activities to provide the chain of possession and custody of any
sample offered for evidence, and for which analytical test
results amy be introduced into evidence in any environmental case.
The primary objective of these procedures is to create an accurate
written record which can be used to trace the possession and
handling of the sample from the moment of collection through
analysis and its introduction as evidence.
1. The laboratory director will designate one full-time employee
(usually the laboratory supervisor) as a sample custodian, and one
other person as an alternate. In addition, the laboratory must
provide a sample storage area that is secure and can be locked.
2. All samples will be handled by a minimum possible number of
persons.
3. Only the custodian will receive incoming samples. If he is
absent, the alternate will indicate receipt by signing the
sample transmittal sheets and, (as appropriate), the sample
tags which accompany the samples. The alternate will retain
the transmittal sheets as permanent records.
4. The custodian shall ensure that heat-sensitive, light-
sensitive samples, radioactive, or other sampe materials having
unusual physical characteristics, or requiring special handling,
are properly stored and maintained prior to analysis.
5. Distribution of samples to the section chiefs who are
responsible for the laboratory performing the analysis
shall be made only by the custodian.
6. The laboratory area shall be maintained as a secured area,
restricted to authorized personnel only.
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7. Laboratory personnel are responsible for the care and custody
of the sample once it is received by them and shall be prepared
to testify that the sample was in their possession and view
or secured in the laboratory at all times from the moment it
was received from the custodian until the time that the
analyses were completed.
8. Once the sample analyses are completed, the unused portion
of the sample, together with all identifying labels, must be
returned to the custodian. The returned, tagged sample,
should be retained in the custody room until permission to
destroy the sample is received by the custodian.
9. Samples shall be destroyed only upon the order of the
Laboratory Director, in consultation with previously designated
Enforcement officials, or when it is certain that the information
is no longer required or the samples have deteriorated. The same
procedure is true for tags and laboratory records.
e. EVIDENTIARY CONSIDERATIONS
Reducing chain of custody procedures as well as the various
promulgated laboratory analytical procedures to writing will
facilitate the admission of evidence under rule 803(6) of the
Federal Rules of Evidence (PL. 93-575). Under this statute,
written records of regularly conducted business activities may
be introduced into evidence as an exception to the "Hearsay
Rule" without the testimony of the person(s) who made the record.
Although preferable, it is not always possible to have the individuals
who collected, kept, and analyzed samples testify in court. In
addition, if the opposing party does not intend to contest the
integrity of the sample or testing evidence, admission under the
Rule 803(6) can save a great deal of trial time. For these
reasons, it is important that the procedures followed in the
collection and analyses of evidentiary samples be standardized
and described in an instruction manual which, if need be, can be
offered as evidence of the "regularly conducted business activity"
followed by the lab or office in generating any given record.
In criminal cases however, records and reports of matters
observed by police officers and law enforcement personnel are not
included under the business record exceptions to the "Hearsay Rule"
previously cited (see Rule 803(8), P.L. 93-595). It is arguable
that those portions of the compliance inspection report dealing
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with matters other than sampling and analysis results come within
this exception. For this reason, in criminal actions records and
reports of matter observed by field investigators may not be
admissible and the evidence may still have to be presented in
the form of oral testimony by the person(s) who made the record
or report, even though the materials come within the definition
of business records. In a criminal proceeding, the opposing
counsel may be able to obtain copies of reports prepared by
witnesses, even if the witness does not refer to the records
while testifying, and if obtained, the records may be used for
cross-examination purposes.
Admission of records is not automatic under either of these
sections. The business records section authorizes admission
"unless the source of information or the method or circumstances
or preparation indicate lack of trustworthiness," and the caveat
under the public records exception reads "unless the source of
information or other circumstances indicate lack of trustworthiness".
Thus, whether or not the inspector anticipates that his or her
compliance inspection report will be introduced as evidence, he or
she should make certain that the report is as accurate and objective
as possible.
14. SPECIFIC GUIDAFCE
American Public Health Association, American Water Works Association,
and Water Pollution Control Federation. 1975. Standard Methods
for the Examination of Water and Wastewater. 14th Edition.
Washington, D.C.
American Society for Testing and Materials. 1978. Annual Bood of
ASTM Standards, Part 31: Water. Philadelphia, Pennsylvania.
Bicking, C., Olin, S., and King, P. 1978. Procedure for the Evaluation
of Environmental Monitoring Laboratories. U.S. Environmental
Protection Agency, Environmental Monitoring and Support Laboratory,
Office of Research and Development, Cincinnati, Ohio.
EPA-600/4-78-017.
Codified Federal Regulations: 40 CFR Part 35, 50, 51, 52, 53, 58,
136, 141 and 250.
Harris, D.J. and Keffer, E.J., June 1974. Wastewater Sampling
Methodologies and Flow Measurement Techniques. U.S. EPA,
Region VII, Kansas City, Missouri. EPA-907/974-005.
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Kulin, Gershon. May 1975. A Guide to Methods and Standards for the
Measurement of Water Flow. U.S. Government Printing Office,
Washington, D.C. National Bureau of Standards Special
Publication 421.
Lauch, R.P. April 1975. Peformance of ISCO Model 1391 Water and
Wastewater Sampler. U.S. Environmental Protection Agency,
Cincinnati, Ohio. EPA-670/4-75-003.
Lauch, R.P. April 1975. Application and Procurement of Automatic
Wastewater Samplers. U.S. Environmental Protection Agency,
Cincinnati, Ohio. EPA-670/4-75-003.
Lauch, R.P. September 1976. A Survey of Commercially Available
Automatic Wastewater Samplers. U.S. Environmental Protection
Agency, Cincinnati, Ohio. EPA-600/4-76-051.
Linen, A.L. 1973. Quality Control for Sampling and Laboratory
Analysis. In: The Industrial EnvironmentIts Evaluation and
Control, pp. 277-297. U.S. Department of Health, Education,
and Welfare, Public Health Service, Center for Disease Control,
National Institute for Occupational Safety and Health.
Sherma, J. 1979 (1st revision). Manual of Analytical Quality Control
for Pesticides and Related Compounds in Human and Environmental
Samples: A compendium of Systematic Procedures Designed to
Assist in the Prevention and Control of Analytical Problems.
Prepared for U.S. Environmental Protection Agency, Office of
Research and Development, Health Effects Research Laboratory,
Research Triangle Park, North Carolina. EPA-600/1-79-008
Smoot, C.W. November 1963. Orifice Bucket for Measurement of Small
Discharges from Wells. Water Resources Division Bulletin,
Illinois Water Survey, Champaign, Illinois.
U.S. Army. Environmental Effects Laboratory. May 1976. Ecological
Evaluation of Proposed Discharge of Dredged or Fill Material
Into Navigable Waters: Interim Guidance for Implementation
of Section 404(b)(l) of Public Law 92-500 (FWPCA of 1972).
U.S. Army Engineer Waterways Experiment Station, Vicksburg,
Mississippi. Miscellaneous Paper D-76-17.
U.S. Department of Interior. Bureau of Reclamation. 1974. Second
Edition, Revised. Water Measurement Manual, U.S. Government
Printing Office, Washington, D.C.
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108
U.S. Environmental Protection Agency, n.d. EPA Project Officer's
Guide (Research & Demonstration Grants). U.S. Environmental
Protection Agency, Office of Planning and Management, Office of
Administration, Grants Administration Division, Washington, D.C.
U.S. Environmental Protection Agency, n.d. Guidance Package for
Evaluation of State Laboratories (Source Sampling)Draft.
Cincinnati, Ohio.
U.S. Environmental Protection Agency. 1976. Minimal Criteria and
Procedures for the Evaluation of Ambient Air Monitoring
ProgramsLaboratory and Field. Draft III.
U.S. Environmental Protection Agency, Enforcement Division. Office
of Water Enforcement. Compliance Branch, n.d. NPDES Compliance
Sampling Manual. Washington, D.C. MCD-51.
U.S. Environmental Protection Agency. Health Effects Research Lab-
oratory. Environmental Toxicology Division. 1974, 1977 rev.
ed. Analysis of Pesticides Residues in Human and Environmental
Samples: A Compilation of Methods Selected for Use in Pesticide |
Monitoring Programs. Edited by J.F. Thompson. Research Triangle
Park, North Carolina.
U.S. Environmental Protection Agency. Office of Research and Development.
Environmental Monitoring and Support Laboratory. 1976. Quality
Assurance Handbook for Air Pollution Measurement Systems:
Volume IPrinciples. Research Triangle Park, North Carolina. |
EPA-600/9-76-005.
U.S. Environmental Protection AGency. Office of Research and Development.
Environmental Monitoring and Support Laboratory. 1977. Quality
Assurance Handbook for Air Pollution Measurement Systems:
Volume 11--Ambient Air Specific Methods. Research Triangle I
Park, North Carolina. EPA-600/4-77-027a. I
U.S. Environmental Protection Agency. Office of Research and Development, m
Environmental Monitoring and Support Laboratory. 1977. Quality I
Assurance Handbook for Air Pollution Measurement Systems:
Volume IllStationary Source Specific Methods. Research
Triangle Park, North Carolina. EPA-600/4-77-027b.
U.S. Environmental Protection Agency. Office of Research and Development.
Environmental Monitoring and Support Laboratory. 1978.
Environmental Radioactivity Laboratory Intercomparison Studies I
Program, 1978-1979. Las Vegas, Nevada. EPA-600/4-78-032.
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U.S. Environmental Protection Agency. Office of Research and Development.
Environmental Monitoring and Support Laboratory. 1979. Handbook
for Analytical Quality Control in Water and Wastewater Lab-
oratories. EPA-600/4-79-019.
U.S. Environmental Protection Agency. Office of Research and Development.
1978. Manual for the Interim Certification of Laboratories
Involved in Analyzing Public Drinking Water Supplies, Criteria
and Procedures. EPA-600/8-78-008.
U.S. Environmental Protection Agency. Office of Research and Development.
Environmental Monitoring and Support Laboratory. 1979. Methods
for Chemical Analysis of Water and Wastes. Cincinnati, Ohio.
EPA-600/4-79-020.
U.S. Environmental Protection Agency. Office of Water Planning and
Standards. Monitoring and Data Support Division and Environmental
Monitoring and Support Laboratory. Minimal Requirements for a
Water Quality Assurance Program, Cincinnati, Ohio. EPA-440/9-75-010,
Weber, C.I., ed. 1973. Biological Field and Laboratory Methods for
Measuring the Quality of Surface Waters and Effluents. U.S.
Environmental Protection Agency, National Environmental Research
Center, Office of Research and Development, Cincinnati, Ohio.
EPA-670/4-73-001.
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aboratory
hiaf, Ross
APPENDIX 3 (Continued)
SlF.VEILLAfiCE ft ANALYSIS DIVISION
U.S. EPA - REGIOM V
ORGANIZATION CHART
Director, Sanders
Deputy Dlr., Yeatcs
ArininistratiVQ Officer,
' Johanssn
Qua!ity
Assurance
Office
Chief, Adams
Environmental
Emergency
Investigations
Branch
Technical"
Support
Branch
Chief, Townsend
Central
District
Office
Chisf, flog an
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Office
Chief. Vacant Chief, WLnkTliofc
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APPENDIX 4
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I STATE OF WIXONSIN
DEPARTMENT OF NATURAL RESOURCES
BUREAU OF AIR MANAGEMENT
AIR MONITORING SECTION
QULITY ASSURANCE MANUAL
| PROCUREMENT
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Procurement Testing Procedures
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The following guidelines are to be used when evaluating continuous
monitors prior to purchase. These are not purchase specifications.
Articles relating to vendor responsibility and warranty obligations will
be included in purchase specification guidelines. This is a description
of parameters that must be considered and tested when evaluating monitors
prior to purchase.
Pre-purchase instrument evaluation will consist of several parts: 1) a
preliminary elimination process based on data gathered by DNR concerning
user experience, vendor provided performance test results, and instrument
advantages and disadvantages; 2) equipment testing of instruments,
selected as a result of screening of data gathered in #1, to assure the
instruments perform as stated - this testing will be performed by DNR
personnel; and 3) final considerations of equipment usability in DNR's
network, vendor cooperation and desirable features, which will further
narrow down the number of instruments. Monitors to be considered for
evaluation must have been designated by EPA as reference or equivalent
methods. No equipment will be approved for purchase without first
having completed the evaluation process outlined here. Final selection
of instruments to be purchased by DNR will be based on the degree to
which the monitor exceeds minimum specifications, the performance test
results, purchase and annual operations costs, and availability and cost
of service/repair by contract/demand.
NEED ANALYSIS
To begin the analysis, the DNR group undertaking the instrument evaluation
must prepare a needs analysis report which analyzes the application for
which the instruments will be used and determines which instrument
characteristics will best fit the application. For example, will the
instrument be used for background monitoring (list the ambient levels
expected) or point source monitoring (expected ambient levels are higher).
The following parameter needs must be defined in this report:
1. expected concentration range
2. threshold concentration
3. anticipated gas stream composition
4. response time
5. maintenance requirements
6. portability requirements
This report is to be prepared and circulated to each DNR group who will
be affected by the instrument purchase, as well as to the Quality Assurance
Coordinator, for comments. After comments are received and the report
revised, the specifications and user review can take place.
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SPECIFICATION AND USER REVIEW
QA 6.2.1.1 I
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|
This phase of the evaluation is a weeding out process. As we have ^-^^
neither the manpower nor space for extensive instrument testing, only a
small number of instruments will be chosen for such testing. This
initial evaluation is to be the means of choosing which instruments will
be tested in-house. If more than one measurement principle is listed as I
a reference or equivalent method (as is the case with SO continuous I
methods) at least one instrument from each measurement principle must be
considered in this initial evaluation. The following information must
be gathered for each instrument that is evaluated, and a report prepared
on the results of this data gathering phase.
1. Request instrument operating manuals from each manufacturer I
and review them. Check and compare measurement principles, I
performance characteristics and relative complexity of operation.
List advantages and disadvantages of each.
2. User experience - The manufacturer will be contacted to supply
a list of users. EPA should also be contacted for names of
any dissatisfied users. Agencies or industries with prior I
field experience with each particular instrument will be
contacted for their opinion of the instrument's mechanical,
electronic and chemical dependability (confidence in instrument
data), ease of working with the instrument, user experience |
with the vendor, vendor responsiveness, cost of operation, and
instrument downtime. At least two users must be contacted for
. each instrument evaluated. Attached is a copy (Figure 1) of
the questions to be covered when talking to the users.
3. Performance testing - Manufacturer shall provide written
results of their equivalency testing, to be evaluated for |
precision, accuracy, interferences, etc.
4. Vendor cooperation - Each vendor will be contacted and evaluated I
as to his/her: a) willingness to comply with the terms of the
pre-purchase arrangement (our in-hour testing) and purchase
contract specs, b) factory and local representative expertise,
support, and facilities, c) instrument warranty terms, d) |
willingness to supply all information required to operate,
maintain and repair the instrument. _
5. Required support equipment - Determine what is needed in terms
of supporting electronics, gas cylinders, etc., for each
instrument evaluated, and the availability and cost of such.
Which of these items do we already have, their adequacy and |
their age. Which items must be purchased and the cost of the
purchase should be included. _
6. Annual operating costs - Approximate cost of parts, reagents,
electronics, gas cylinders, manpower support, and a list of
high and low motality parts for each instrument evaluated.
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7. Conformity of each instrument to existing DNR instrumentation
systems (both the vans and the permanent continuous monitoring
stations).
a. manifold .
b. data acquisition system
c. rack mounting
d. calibrators
«
The information in the report will be organized into tables for purposes
of comparison; each parameter listed above is to be scored (based on its
relative importance as determined in the needs analysis) and a summary
chart of comparative scores will be drawn up. These tables and charts
will be circulated for comment and recommendations to key persons within
the air monitoring program who are knowledgeable with instrumentation.
Any instrument or manufacturer not favorably rated in this phase of
evaluation will be excluded from further testing. Recommendations for
no more than three instruments to be tested in depth in DNR labs, will
be made by representatives of each monitoring group and the quality
assurance coordinator.
INSTRUMENT TESTING
As a result of the specification and user review, up to three monitors
will be tested in-house by DNR personnel.
The purpose of this testing is to:
1. Obtain a working knowledge of each instrument - how easy it is
to use, how well it performs, and what problems we might
expect with it.
2. Verify that certain crucial equivalency testing parameters are
indeed met; Equivalency test results are provided to EPA by
the manufacturer and are not verified by EPA. Some users have
found that the equivalent designated instruments that they
have purchased are not meeting these performance specifications.
3. There are differences in instrument performance among instrument
manufacturers whose instruments pass the equivalency specifications.
Some instruments just pass the testing, while others have
performance that is vastly superior to the equivalency specifications.
The following instrumental tests are to be conducted on all continuous
monitors being considered for purchase. Figure 2 is an example of how
the results of the testing should be reported.
I. Range
A. Definition
- - es
Nominal minimum and maximum concentrations which a method is
capable of measuring.
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B. Test Procedure
1. Allow the instrument to warm up as per manufacturer's
instructions.
2. Construct a calibration curve showing the test analyzer's
response over at least 95 percent of the required range.
3. Allow the instrument to run for 24 hours before performing
any further tests.
II. Noise Test
A. Definition
Noise is the short-term deviation in output signal which is
not the result of changes in input concentration. It is
essentially the standard deviation. Noise is an inherent
" property of an instrument arising from imperfect electronics,
mechanical stresses, quality of optics, etc. Noise levels are
critical as they set limits on useful measurement levels, and
the lower detectable limit is often defined as twice the noise
level.
B. Test Procedure
1. Allow sufficient time for the test analyzer to warm up
and stabilize.
2. Connect an integrating-type digital voltmeter (DVM)
suitable for the test analyzer's output, and accurate to
three significant digits, to measure the analyzer's
output signal. Also connect the analyzer to an appropriate
strip chart recorder.
3. Measure zero air for 60 minutes. Use the range setting
specified in Table I. The recorder should be set for 0
to 1 volt full scale. During this 60-minute interval,
record 25 readings at 2-minute intervals.
4. Convert each DVM reading or strip chart recording to
concentration units (ppm) by reference to the test
analyzer's calibration curve. Label the converted DVM
readings r^, r£, »
5. Calculate the standard deviation, S, as follows:
2 - 1/25 ^±)
S (ppm)
24
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6. Let S at zero ppm be So; compare So to the noise specification
given in Table I.
7. Repeat steps (3) through (6) using a recorder output of
either 0 to 1MV or 0 to 5MV. The baseline on the strip
chart should be at 50% of full scale, so that positive
and negative deviations can be observed. Compare S^y to
the noise specification as given in Table I.
C. Lower Detectable Limit
Definition - The minimum pollutant concentration which produces
a signal of twice the noise level.
1. Test Procedure
a. Allow sufficient time for analyzer to warm up and
stabilize. Measure zero air for at least 15 minutes
and record the stable reading in ppm as BZ-
b. Generate and measure for at least 15 minutes a
pollutant test atmosphere concentration equal to the
value for the lower detectable limit specified in
Table I.
c. Record the test analyzer's stable indicated reading,
in ppm, as B^.
d. Determine the lower detectable limit (LDL) as LDL »
Bl ~ BZ' Compare BL - BZ to 2SO.
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1
1
Table I - EPA Performance Specifications for Automated Methods
Sulfur Photo- Carbon
Performance parameter Units dioxide chemical monoxide
oxidants
1. Range - Parts 0-0.5 0-0.5 0-50
per
million
2. Noise do ^ .005 .005 .50
3. Lower detectable
limit do .01 .01 1.0
4. Interference
equivalent
Each inter ferent do +.02 +.02 +1.0
Total interferent do .06 .06 1.5
5. Zero drift,
12 and 24 hour do +.02 +.02 +1.0
6. Span drift, 24 hour
20 percent of upper
.range limit Percent +20.0 +20.0 +10.0
80 percent of upper
range limit do +5.0 +5.0 +2.5
7. Lag time Minutes 20 20 10
8. Rise time do 15 15 5
9. Fall time do 15 15 5
10. Precision
20 percent of upper
range limit Parts
per
million .01 .01 .5
80 percent of
upper range limit do .015 .01 .5
1. To convert from parts per million to ug/m^ at 25°C and
multiply by M/0. 02448, where M is the molecular weight of
t
-
as
-
.
Nitrogen
dioxide
0-0.5
.005
.01
+0.02
.04
+.02
+20.0
+5.0
20
15
15
.02
.03
760 mm Hg,
the gas.
-
1
1
1
1
1
1
1
1
1
1
1
1
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III. Zero Drift, Span Drift, Lag Time, Rise Time, Fall Time and Precision
Test "-^
(Also may indicate voltage variation and ambient temperature sensitivity)
*
A. Definitions
Zero Drift - This value is the change in response to zero
pollutant concentration over a 24 hour period of continuous
unadjusted operation.
Span Drift - This value is the percentage change in response
to pollutant concentrations of 80% of scale and 20% of scale
over a 24 hour period of continuous unadjusted change.
Lag Time - The time interval between a change in pollutant
concentration input and a corresponding change in scale readings.
Rise Time - The time interval between an increase in pollutant
concentration input and 95% response to a new concentration
level.
Fall Time - The time interval between a decrease in pollutant
concentration input and 95% response to the new concentration.
Precision - Precision is defined as a variation about the mean
of repeated measurements of the same pollutant concentration
expressed as one standard deviation about the mean.
B. Test Procedure - The monitor should be set up in such a manner
that the voltage and temperature may be controlled (or recorded)
and, if possible, altered experimentally to levels the monitor
may be expected to encounter. If the instrument is to be
housed in a tightly controlled environment, the monitor need
be tested only in a duplication of that environment. This
test procedure need only be performed once if the instrument
is to be used in a controlled environment; at least three test
runs must be performed at varying environmental conditions if
the instrument will be subject to voltage and temperature
fluctuations at a monitoring site. In either case, more
testing should be done if the instrument responds irregularly.
During this procedure no manual adjustments to the electronics,
gas or reagent flows, other than those specified by the test,
or as part of a required periodic maintenance program, is to
be performed.
The instrument shall be operated at 115 volts and at
25°C.
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1. Allow sufficient time for instrument warm-up and
stabilization. Adjust the zero baseline to 5 percent
of full scale. Recalibrate if necessary. (Usually
if the span check indicates a span drift in excess
of the value listed in Table I.)
2. Arrange to generate test atmospheres as follows:
Test Atmosphere Pollutant Concentration (Percent)
URL » Upper range limits
A0 " Zero gas
A2Q 20 + 5 of URL
A3Q 30 + 5 of URL
ABO 80 + 5 of URL
Ago ' 90 + 5 of URL
Set chart speed at 2 inches/hr.
3. Measure AQ until a stable reading is obtained.
Record reading as Z!Q. Note the clock time on the
strip chart.
4. Measure &2Q until a stable reading is obtained.
Record reading as M^-Q. Note the clock time on the
strip chart.
7 5. Measure Ag« until a stable reading is obtained.
Record reading as S^-Q. Note the clock time on the
strip chart.
6. Sample Ag until reading is less than 15 percent of
full scale. A stable reading is not required.
7. Measure A2Q- Record stable reading as P^.
8. Sample A3Q. A stable reading is not required.
9. Measure A2Q- Record stable reading as P2-
10. Sample AQ. A stable reading is not required.
11. Measure A2Q. Recor(* stable reading as P^.
12. Sample A3Q. A stable reading is not required.
13. Measure A2Q- Record stable reading as P^.
14. Sample An. A stable reading is not required.
15. Measure A2Q» Record stable reading as PS- -
16. Sample A3Q. A stable reading is not required.
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I 17. Measure A2g. Record stable reading as Pg. Note the
\ clock time on the strip chart.
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18. Measure AQQ. Record stable reading as Py.
19. Sample Agg. A stable reading is not required.
20. Measure Agg. Record stable reading as Pg. Set
chart speed at 4 inches/hr.
21. Measure AQ. Record stable reading as L]_.
22. Quickly switch test analyzer to measure Agg. Mark
recorder chart at exact time of switch.
23. Measure Agg. Record stable reading as Pg.
24. Sample Agg. A stable reading is not required.
25. Measure AQQ. Record stable reading as P^g.
26. Measure AQ. Record stable reading as L2>
27. Measure Agg. Record stable reading as PJJ_.
28. Sample AQ. A stable reading is not required.
29. Measure Agg. Record stable reading as P^- Note
the clock time on the strip chart.
30. Measure AQ. Record stable reading as Z-,. Note the
clock time on the strip chart.
31. Measure A2g. Record stable reading as M^.
32. Measure Agg. Record stable reading as S^.
33. Zero Drift
Zero Drift - zk> - Z^
Report the Elapsed Testing Time as Measured in Steps
(3) and (30).
34. Span Drift
(a) at 20% URL
Span Drift - ^a - Mo x 100%
~
where:
Report the Elapsed Testing Time as Measured in Steps (4) and (17).
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(b) at 80% URL
Span Drift
S - S
n ox 100%
where:
o
12
s-l if,',
Report the Elapsed Testing Time as Measured in Steps
(5) and (29).
35. Lag Time
Determine from the strip chart, the elapsed time in
minutes between the mark made in step 22 and the
first observable (2 x noise level) response.
36. Rise Time
Calculate 95 percent of reading Pg and determine
from the recorder chart the elapsed time between the
first observable (2 x noise level) response and a
response equal to 95% of Pg.
37. Fall Time
Calculate 95 percent of (P10 - L2) and determine the
elapsed time in minutes between the first observable
decrease in response following PIQ and the response
equal to 95 percent of (P^Q - L2).
38. Precision
Calculate precision (?2Q an<*
(a)
P20 ^
as follows:
-f6 2 ~(< \
80
1 fl2 " 1 /12 \2
5 £ pJ-6 £P,
Li-7 i \±-7 *] ^
Obtain a stable zero air reading. Record. Introduce a
test atmosphere of 80% of scale. Allow instrument to run
and record at this level for 24 hours. At the end of the
24 hour period, return to zero air and obtain a stable
reading. Report the ppm value for the first hourC^) and
for the last hour (X2) . Report span drift (80%) as X? -
IQQ
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3. Day 3
After obtaining and recording the zero air reading,
introduce a 20% of scale test atmosphere. Allow instrument
to run and record at this level for 24 hours. Return to
zero air and record the stable reading. Report the ppm
value for the first hour (Y^) and for the last hours
Report span drift (20Z) as Y£ - Yj ^QQ
4. Day 4
Repeat day 2 procedures, except allow instrument to run
for 48 to 72 hours.
5. Day 6
Repeat day 4 procedures, except use zero air.
If the instrument will be operated under conditions of fluctuating
temperatures and voltages, repeat this test procedure (beginning
with Day 1) at least two more times, altering ambient temperatures
and voltage levels to settings the instrument is likely to
encounter in the field.
IV. Interference Test
A. Definition - Interference is the positive or negative effect
of a substance, other than the pollutant being measured, as
reflected in instrument response.
B. Test Procedure - The test procedure will vary depending on the
instrument and its potential interferences. The procedures to
be used will be written by the QA Coordinator (in conjunction
with the testing group) prior to the beginning of the testing
phase.
V. Flow Rate Measuring Device - Factors to be taken into consideration
are the accuracy of the device, ease of calibration (either in or out of
the sampling line), ease of adjustment and flow rate drift. Data from
this test should be recorded as in Figure 3.
A. x Test Procedure -
1. Calibrate the flow rate controller, as specified in the
instrument operation's manual, with a transfer standard of
known high accuracy (such as a wet test meter, soap bubble
meter or mass flow meter). Thereafter, run a daily flow rate
check of one or more points to check the flow rate controller's
stability. Report the maximum 7. deviation in the flow rate
calibration.
2. Record the flow rates each day, as indicated on the
instrument's flow rate measuring devices for each parameter of
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interest (H2 flows, sample flows, etc.). Report the maximum %
variability in the flow rate readings for each parameter
measured.
For further details regarding any of the above tests, please refer
to the February 18, 1975 Federal Register - Ambient Air Monitoring
Reference and Equivalent Methods Fart II.
VI. Calibration Drift
When all testing is complete, run a multipoint calibration of the
analyzer. DO NOT ADJUST ZERO OR SPAN SETTINGS ON THE INSTRUMENT.
Compare with the initial calibration as follows:
A. Determine the slope and intercept for each calibration; X »
ppm, Y = instrument reading.
B. Using the slope and intercept for each calibration determine
the ppm values at each instrument reading from 10 to 100% in
units of 10 (see Figure 5).
C.. Determine the percent differences for each ppm value obtained
in B. Assume the initial calibration value is the "true
value." _
D. Report the average percent difference as:
i
I Diff - 1=1 di
'Note that the absolute values of the percent differences are
used.
E. Report the maximum percent deviation observed in the region in
which ambient concentrations will fall. Report this data on
Figures 4 and 5. Instructions for completing Figure 4 precede
the figure.
A report must be prepared which includes all the original data, strip
charts, calculations and calibrations. In addition, the calculated
data - span drifts, calibration drifts, etc., should be organized into
tables for purposes of comparison. The following areas determined in
the "Specification and User Review" and in the "Instrument Testing"
should be included in this report.
1. Vendor Cooperation
a. willingness to comply with terms of DNR prepurchase
and purchase specifications.
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supplier) purchase of parts. Specify parts available
only from vendor.
d. instrument delivery time for all ordered monitors
e. condition of the monitor when received for "instrument
testing"
f. warranty terms
2. Required support equipment - What is needed in terms of
supporting electronics, gas cylinders, etc. and availability
of such. Detail which items we already own and which
would have to be purchased.
3. Annual operation's cost - Approximate cost of parts,
reagents, electronics, gas cylinders and manpower support.
4. Operations Manual
a. ease of comprehension
b. completeness (including wiring blue prints)
5. Ease of Access for:
a. instrument repair
b. routine maintenance
c. hook up, either free standing or rack mounted
d. routine calibration
e. of knobs, switches, and dials
6. Conformity to Existing Instrumentation Systems
a. manifold
b. data acquisition system
c. rack mounting
7. Aesthetic Appeal
Consideration of where and how instrument is to be used should be kept
in mind in making a subjective evaluation. Where problems are specific
to a certain use of the instrument (ex. if used in the vans it's a
problem) specify this in describing the problem.
The report should be completed within 30 days of the end of the project.
It should then be circulated for comment and recommendations to key
persons within the monitoring program who are knowledgeable in this
area. The report should also be forwarded to the Bureau for filing. A
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final decision as to instrument purchase should be made within two
weeks. The decision will be made at a conference (phone or personal)
with representatives of each monitoring group and the QA Coordinator.
NOTE;
When a decision on instrument purchase must be made rapidly, a shortened I
version of this report - just containing the charts and tables from the
evaluations should be circulated for comment immediately. The remainder
of the report is still to be written and added to the tables at a later
date. . I
A sample copy of a procurement report is available from the Quality
Assurance Coordinator.
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»
FIGURE 1
AMBIENT AIR ANALYZERS
USER FACT SHEET
INSTRUMENT MANUFACTURER AND MODEL NUMBER
COMPANY NAME DATE
COMPANY CONTACT PHONE NUMBER
DNR CONTACT
1. GENERAL INFORMATION
a. How many analyzers do you own?
I b. How long have you operated the analyzers?
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2. MECHANICAL DEPENDABILITY
| a. In the time since you have owned the instruments, how many
mechanical breakdowns, on average, have you experienced?
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b. Do any specific parts give more breakdown problems than
. others? If so, which ones?
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3. ELECTRONIC DEPENDABILITY
In the time since you have owned the instruments, how many
electronic breakdowns, on average, have you experienced?
4. CHEMICAL DEPENDABILITY
a. What is the average zero and span drift you see on the
instrument - in ppm/x days or in Z chart/x days?
b. How frequently do you perform zero/span checks?
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b. Do any specific parts give more breakdown problems than
others? If so, which ones?
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c. How frequently do you have to perform a multipoint cali-
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e. What is the response time on the instrument - in minutes or
seconds - to reach 95Z of scale from the baseline?
5. EASE OF WORKING WITH THE INSTRUMENT
* QA 6.2.1.1
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. Page 17 of 28
d. How long does it take to perform the multipoint calibration?
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* a. Are the control switches and knobs easily accessible to
the operator?
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b. How easy is it to
1. replace boards?
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3. replace filters or other parts?
Be specific (example: flow controllers cannot be reached
without dismantling...etc.).
I)
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6. VENDOR RESPONSIVENESS
b. What is the quality of the repair work performed by the
vendor or manufacturer? Be specific.
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How sophisticated mist the user be to operate the instrument?
Can an engineer operate it? An electronics technician? A ^^^ H
chemist? I
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What is the turnaround time on vendor repair of instruments?
Be specific - in days, weeks, etc. I
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How long does it take to get a. vendor or manufacturer repair _
person to the field?
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\ d. Are vendor representatives knowledgeable about the instrument,
Jm Its operation and potential problems?
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7. COST 07 OPERATION
I a. What parts, chemicals or other equipment must be replaced
frequently?
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b. How expensive are replacement parts? Be specific.
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c. Row much time must be spent by repair people, operators,
electronics people, chemists, etc., to keep the instruments
"" operational?
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rage zu or zo
8. INSTRUMENT DOWN TIME
What percent data capture do you average, or how many hours/unit
time (day, month, etc.) are the instruments inoperable?
9. INTERFERENCES
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b. What is the major reason for your instrument down time? '
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a. Are there any common interferences (gases in the ambient
. air, at the site; temperature variations, etc.) which affect
the response of the instrument? If yes, what are they? I
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b. Bow badly is the instrument affected by the interferents?
Be specific.
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M 10- GENERAL INFORMATION
; ^v
I a. Have you used any other manufacturer's analyzers? If yes,
which ones?
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b. If you had a choice, would you purchase this analyzer again?
Why?
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c. Any other comments not covered above.
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. ' FIGURE 2
, AMBIENT AIR ANALYZERS
} INSTRUMENT PERFORMANCE DATA SHEET
t
Instrument Manufacturer
and Model #
Instrument Serial #
EPA PERFORMANCE SPECIFICATIONS
Range
Noise
Lower Detectable Limit
Interferent Equivalent
24 hrs.
Zero Drift
Span Drift
-"
Lag Time
Rise Time
. Fall Time
" Precision
5,'
Date
Pollutant
. PERFORMANCE SPECIFICATION RESULTS
(Minimum)
(Maximum)
(So)
(SHV)
(B.-B,)
(2x noise)
(Interferents(s))
Result
24 hrs 48 hrs 72 hrs
24 hrs 48 hrs 72 hrs
20%URL
80HJRL
>
._ _ PO«
1
1
1
1
1
1
1
1
1
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Instrument Manufacturer
and Model Number
Calibrator S/N#
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Recorder Zero Setting
Zero Setting
Span Setting
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. FIGURE 3
PERFORMANCE SPAN AND FLOW RATE CHECKS
Analyzer S/Ntf
Last Generator Calibration
Date
Rotameter
Setting
Flow
cc/min
Calibration Output
Analyzer Response
.
\
Sample
Flow Rate
*Z Diff .
*Z Diff.
Analyzer Response - Calibration Output A 100Z
Calibration Output /
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Auxiliary Gas Flow Rate
(Specify gas)
Remarks:
Method(s) of Analyzer Data Retrieval
Strip Chart
Data Averages _____
Data Logger
How was sample flow rate determined?
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CALIBRATION FORM
revision 0
Page 24 of 28 |
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1. Instrument manufacturer and model number - The manufacturer's
name, the model number of the analyzer. _
2. Instrument number - The manufacturer's serial number affixed to
the analyzer. <
3. Initial calibration date - Date of the first calibration of the |
analyzer.
By - Name of person performing the calibration.
4. Final calibration date - The date of the final calibration of the
analyzer.
By - The last name or initials of the person performing the
calibration. tm
5. Generator number - The DNR serial number for the generator used to
calibrate the analyzer.
6. Date of last generator calibration - The date the generator was I
calibrated.
7. Remarks - Any comments on instrument performance that would affect
the interpretation of the calibration data.
8. This information is completed for all analyzers. I
a; Sample flow rate - The sample air rotameter setting.
b. Auxiliary gas flow rate - Flow rate of any gases used by
the analyzer (example; air, hydrogen, ethylene).
Zero setting - If the instrument is so equipped, this is
the reading on the zero control setting.
I
Span setting - The reading from the span setting. _
d. Zero offset - The Z chart reading when zero volts is applied
to the recorder.
9. Number 8 is completed twice for each instrument calibration. The
values for each parameter are entered into the INITIAL column when
the instrument is first calibrated, and each parameter is then
recorded in the FINAL column when the final calibration is com-
pie ted.
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There are eight columns on the bottom half of the form. These are
completed for both INITIAL and FINAL calibrations.
1. Generator setting - In this column place first the number on the
lamp position switch if ozone is used. After it, place the rotameter
setting.
2. Generator concentration ppm - The output from the generator for the
rotameter setting and position switch setting used.
3. Initial chart reading. Z FS - This column lists the Z chart reading
for the pollutant value in column 2 when the Instrument has the
span setting found in the INITIAL column.
4. Initial instrument reading ppm - This is the instrument reading
found on the instrument panel when a given quantity of pollutant
is passed to it.
5. Final chart reading Z FS - This column lists the Z chart reading
for the pollutant value in column 2 when the instrument has the
span setting found in the FINAL column.
6. Final instrument reading ppm - This is the instrument reading for
a given quantity of pollutant at the FINAL calibration.
7. Percent - This is the percent deviation of the instrument from the
true pollutant concentration. It is calculated twice. The top
half of the column gives the initial percent. This is defined as:
Generator ppm - Initial reading x 100
Generator ppm
or
Column 4 - Column 2 x 100
Column 2
The bottom half of the column lists the final percent. This is
defined as:
Generator ppm - Final reading x 100
Generator ppm
or
Column 6 - Column 2 x 100
Column 2 . .
. -.; .'"""''."-. "'"--- - - - - t- -
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INSTRUMENT MANUFACTURER
AND MODEL NUMBER
FIGURE 4
CALIBRATION FORM
INSTRUMENT
INITIAL CALIBRATION DATE
BY
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NUMBER
FINAL CALIBRATION DATE BY
GENERATOR NUMBER
REMARKS:
DATE OF LAST GENERATOR CALIBRATION
SAMPLE FLOW RATE
INITIAL FINAL
CALIB. CALIB.
AUXILIARY GAS FLOW RATE
(SPECIFY GAS)
ZERO SETTING
ZERO OFFSET
(Z CHART)
SPAN SETTING
OTHER (SPECIFY)
GENERATOR SETTING
POSITION
SWITCH
(
ROTO /
SET. sS
./FLOW
S (CC/MIN)
L)
~"
GENERATOR
POLLUTANT
PPM
(2)
-
INITIAL
CHART
READING
(Z FS)
(3)
INITIAL
INSTRU.
READING
ppb
(4)
FINAL
CHART
READING
(Z FS)
(5)
FINAL
INSTRU.
READING
ppb
(6)
-
An /
INITIAL/
/ AZ
/ FINAL
COMMENTS
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
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4 Z INITIAL - Col. A-Col. 2
Col. 2
4 Z FINAL - Col. 6-Col. 2
Col. 2
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FIGURE 5
CALIBRATION DRIFT TEST
INITIAL SLOPE FINAL SLOPE
INITIAL INTERCEPT FINAL INTERCEPT
DATE OF CALIBRATION . DATE OF CALIBRATION
AVG. Z DIFFERENCE
INITIAL FINAL I
Z CHART VALUE VALUE DIFFERENCE
10
20
30
50
60
70
80
90
100
Z DIFF. - FINAL VALUE - INITIAL VALUE x 100
INITIAL VALUE
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1
1
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1
1
1
1
1
1
1
1
1
1
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1
z
z
o
-1 a:
O- > i CD
gLU
Q£ f
LU
00 Q
LU Z
i-v cac
fl.
» f 1
oo « *
^v ,«-^
LU .a
z ^-
H^ *^"
-
iai
i i _i <:
X J
- i i
LU <
t5
O fl-
ea oo
LU
^>
P
/v
LU
OO
LU
Q_
CH
LU
LU
<
CL.
a; .
cu -a si 4->
C L, (/I 3 Q_ [ ^ ^
"S 3 >, S- O J- r-
. r~- to i.
i >, o to aj aj
r 40 S ^* »^- (^ 4^
ia -f- o a. to <+-
o «*- >>i "3
1. .,_ . i
O & TD tO K3 ,
^ W> 4-> J= ^^ y, ^
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APPENDIX 6
EPA OFFICIAL ANALYTICAL METHODOLOGY
PRIOROTY POLLUTANT MEASUREMENTS
Recommended analytical methods for priority pollutants are described
in "Sampling and Analysis Procedures for Screening of Industrial Effluents
for Priority Pollutants" available from the Environmental Monitoring and
Support Laboratory, EPA, Cincinnati, Ohio 45268.
These guidelines for sampling and analysis of industrial wastes have
been prepared by the staff of the Environmental Monitoring and Support
Laboratory - Cincinnati, at the request of the Effluent Guidelines Division,
Office of Water and Hazardous Wastes, and with the cooperation of the
Environmental Research Laboratory, Athens, Georgia. The procedures represent
the current state of the art, but improvements are anticipated as more
experience with a wide variety of industrial wastes is obtained. Users of
these methods are encouraged to identify problems encountered and to assist
in updating the test procedures by contacting the Environmental Monitoring
and Support Laboratory, EPA, Cincinnati, Ohio 45268. These methods were
first made available in March 1977 and were revised-in April 1977.
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APPENDIX 7
EPA OFFICIAL ANALYTICAL METHODOLOGY I
HAZARDOUS WASTE MEASUREMENTS |
1
Samples will be collected in containers prepared by the CRL and
shipped to the National Field Investigation Center - Denver, for
extraction. The extract will be returned to the CRL lab for analysis. |
NEIC expects to be ready to start processing samples in about _
three months. A safety manual for handling these materials which will I
presumably contain information on containers and shipping is also being
prepared.
The collection of samples, preparation of containers, etc., is I
to be coordinated through the Director of the CRL. Existing Agency
test procedures are to be used until test procedures specifically for
the hazardous waste program have been finalized by the Agency. I
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PARAMETER
1 Parti cul ate Filters
| Sulfur Dioxide
(Pararosanili ne Method)
1 Nitrogen Oxides
(Sodium-Arsenite Method)
Fluoride
1
1
1
1
1
1
1
APPENDIX 8
SAMPLE COLLECTION, PRESERVATION, AMD
HOLDING TIMES
AMBIENT AIR SAMPLES
REC OMMENDED
HOLDING TIME PRESERVATION METHOD
Indefinite Store in controlled
atmosphere of <50%
relative humidity
30 days, if Store at <4°C after
properly stored collection, during
transport, and
before analysis
6 weeks Samples are stable
for 6 weeks at room
temperature
None Collect and store
in plastic
containers
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re c .c -r-
a; >-i a, 2:
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APPENDIX 14
Page 1 of 3
SAMPLE COLLECTION CONTAINERS, PRESERVATIVES, AND HOLDING
TIMES FOR SAMPLES COLLECTED IN THE 1412 MONITORING PROGRAM
CHEMISTRY1
I
PARAMETER
PRESERVATIVE2
CONTAINER3
MAXIMUM
HOLDING
TIME4
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Arsenic
Bari urn
Cadmium
Chromium
Lead
Mercury
Nitrate
Selenium
Silver
Fluoride
Chlorinated
hydrocarbon
Chlorophenoxys
Cone. HN03 to pH<2
Cone. HN03 to pH<2
Cone. HNOs to pH<2
Cone. HNOs to pH<2
Cone. HN03 to pH<2
Cone. HN03 to pH<2
Cone. H2$04 to pH<2
Cone. HN03 to pH<2
Cone. HN03 to pH<2
None
Refrigerate at 4°C as
soon as possible after
collection
Refrigerate at 4°C as
soon as possible after
collection
P or G
P or G
P or G
P or G
P or G
G
P
P or G
P or G
P or G
P or G
G with foil or
Teflon lined cap
G with foil or
Teflon lined cap
6 months
6 months
6 months
6 months
6 months
38 days
14 days
14 days
6 months
6 months
1 month
14 days5
7 days^
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1 - If a laboratory has no control over these factors, the laboratory director must
reject any samples not meeting these criteria and so notify the authority
requesting the analyses.
2 - If HNOs cannot be used because of shipping restrictions, samples may be initially
preserved by icing and immediately shipping it to the laboratory. Upon receipt in
the laboratory, the sample must be acidified with concHN03 to pH<2. At time of
analysis, sample container should be thoroughly rinsed with 1:1 HNOs; washings
should be added to sample.
3 - P = Plastic, hard or solf; G = Glass, hard or soft.
4 - In all cases, samples should be analyzed as soon after collection as possible.
5 - Well stoppered and refrigerated extracts can be held up to 30 days.
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PARAMETER
Gross alpha
Gross beta
Stronti um-89
Stronti um-90
Radi um-226
Radium- 228
Cesium-134
Iodine-131
Tri ti um
Urani um
Photon emitters
1 - "Federal Register"
2 - It is recommended
collection unless
sample must be shi
sample (in its ori
5 days. A minimum
3 - P = Plastic, hard
4 - If KH is used to
APPENDIX 14 (Continued)
RADIX HEMISTRY1
PRESERVATIVE2
Cone. H:i or HN03 to pH<24
Cone. H31 or HN03 to pH<24
Cone. K;i or HN03 to pH<2
Cone. KM or HN03 to pH<2
Cone. fCl or HNC^ to pH<2
Cone. hCl or HN03 to pH<2
Cone. H:i to pH<2
None
None
Cone. H31 or HN03 to pH<2
Cone. KT1 or HMOs to pH<2
, Volume 41, No. 133, July 9, 1976.
that the preservative be added to the sample
suspended solids activity i s to be measured,
Page 2 of 3
CONTAINER3
P or G
P or G
P or G
P or G
P or G
P or G
P or G
P or G
G
P or G
P or G
at the time of
However, if the
pped to a laboratory or storage area, acidification of the
ginal container) may be delayed for a period
of 16 hours must elapse between acidificati
or soft; G = Glass, hard or soft.
acidity samples which are to be analyzed for
not to exceed
on and analysis.
gross alpha or
gross beta activities, the acid salts must be converted to nitrate salts
before transfer of
the samples to planchets.
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Page 3 of 3
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APPENDIX 14 (Continued)
MICROBIOLOGY
DRINKING WATER SAMPLES
I Sample bottles must be of at least 120ml capacity, sterile plastic
or hard glass, wide mouthed with stopper or plastic screw cap and capable
| of being sterilized repeatedly. 10mg/l sodium thiosulfate is added to
_ the sample during preparation. Sample volume must be at least 100ml.
Samples must be analyzed within 30 hours after collection. If a State
principal laboratory is required by State regulations to examine samples
after 30 hours and up to 48 hours, the laboratory must indicate that the
data may be invalid because of excessive delay before sample analysis.
Samples arriving 48 hours shall be refused without exception and a new
M sample requested.
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APPENDIX 15
UNITED STATES ENVIRONMENTAL PROTECTION
'vTt' MAR G 1378
;CT-. Approved Alternative Analytical
Methods - Nationwide Use
!OM: victor J. Kimm, Deputy Assistant
Administrator for Drinking Water (WH-550)
T0: All Regional Admjjiistrators
Listed below are additional alternative analytical methods for
nationwide use which I have approved for the National Interim
Primary Drinking Water Regulations. As stated in my March 10,
1977 menorandum on this subject, publication of new alternate
analytical methods will eventually follow in the Federal Register.
Specific questions regarding the details of these procedures
should be directed to the Director, Environmental Monitoring
and Support Laboratory, Cincinnati.
Measurement
Organics (Pesticides)
Fluoride
Fluoride
Method
"Standard Methods for the Examination of
Water and Wastewater,11 14th ed., 1975.
Organochlorine Pesticides, part 509A,
pp. 555-564, Chlorinated Phenoxy Acid
Herbicides, part 509B, pp. 565-569.
Modified Automated Alizarin Blue. Ref:
"Fluoride in Water and Wastewater,"
Industrial Method S129-71W, December 1972,
Technicon Industrial Systems
Tarrytown, NY 10591
Automated Electrode Method, Ref:
"Fluoride in Water and Wastewater"
Industrial Method £380-75WE,
February 2, 1976, Technicon Industrial
Systems, Tarrytown, NY 10591
cc: Water/
S & A
A & H M
A Fr.,,, 1370 I. IR,.v. 3 76)
MAR 1 5 1978
EPA REGION 5
OFFICE OF RCGIONAl
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SUBJE
UNITED
a,.. SEP 11977
AGEHCY
~T: Approved Alternative Analytical
CMthods -Nationwide Use
J. Kimm, Deputy "Assistant
//Administrator for Water Supply (WH-550)
TO: All Regional Administrators
jYCuOrDirty.oi'Ofi
This memorandum replaces my earlier memo of May 10 on this subject,
since questions at the regional/State level concerning its implementation
have been raised. In addition, some points need further clarification
and comment prior to official publication of the approved alternate
analytical methods in the Federal Register.
In order to expedite the publication of these needed alternate analytical
methods and to correct and clarify inaccuracies and other possible
ambiguities which may have occurred as the result of collective actions
the approved methods for nationwide use are summarized below; hence,
iny May 10 memo should be disregarded.
Measurement
Arsenic
Arsenic
Barium
Cadmium
Chromium
Fluoride
Method
Flameless Atomic Absorption, Graphite
Furnace Technique.
Silver Diethyldithiocarbamate Method, Ref:
"Methods for Chemical Analysis of Water and
Wastes, "pp. 9-10, EPA Office of Technology
Transfer, (1974).
Flameless Atomic Absorption, Graphite
Furnace Technique.
Flameless Atomic Absorption, Graphite
Furnace Technique.
Flameless Atomic Absorption, Graphite Furnace
Technique.
Automated Alizarin Fluoride Blue, Ref: "Stan-
dard Methods for the Examination of Water
and Wastewaier," 14, pp. 614-616, (1375)
CPA Fcrm 1310-t fRc». 3-761
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Fluoride
Lead
Mercury
Nitrate
Nitrate
Organics
Selenium
Selenium
Silver
APPENDIX 15 (Continued)
Zirconium-Eriochrome Cyanine R. Ref: "Methods
for Collection and Analysis of Water Samples for
Dissolved Minerals and Gases," USGS, Book 5,
Chapter A 1, pp. 90-93.
Flameless Atomic Absorption, Graphite
Furnace Technique.
Automated Cold Vapor Technique, Ref: "Methods
for Chemical Analysis of Water and Wastes,"
pp. 127-133, EPA Office of Technology Trans-
fer, (1974).
Automated Hydrazine Reduction, Ref: "Methods
for Chemical Analysis of Water and Wastes,"
pp. 185-194, NERC Analytical Quality Control
Laboratory, (1971).
Automated Cadmium Reduction, Ref: "Methods for
Chemical Analysis of Water and Wastes, " pp. 207-
212, EPA Office of Technology Transfer, (1974). I
Gas Chromatographic, Ref: "Methods for Analysis
Organic Substances in Water," USGS, Boo1- 5,v
Chapter A 3, pp. 24-39.
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Hydride generation - atomic absorption
spectrophotometry, USGS. Method, 1-1667-77,
(1976).
Flameless Atomic Absorption, Graphite Furnace
Technique, Ref: Atomic Absorption Newsletter,
14, No. 5, pp. 109-116, (1975).
Flameless Atomic Absorption, Graphite Furnace
Technique.
Once it is published, you will be provided with copies of the FR
notification by my office. In the interim, these methods may be
considered as approved alternative analytical methods to meet the
monitoring requirements of the SDWA. Additional information on
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APPENDIX 15 (Continued
the flameless atomic absorption graphite furnace technique is
available from the Director of the Environmental Monitoring
and Support Laboratory in Cincinnati until the 1974 EPA
manual is updated.
1
The various furnace devices are considered to be atomic absorption
techniques. Methods of standard addition are to be followed as noted
on p. 78 of "Methods for Chemical Analysis of Water and Wastes, "
EPA Office of Technology Transfer, (1974).
2
Copies available from: Water Quality Branch, National Center
U.S. Geological Survey, 112201 Sunrise Valley Drive, Reston,
Virginia 22092.
3
Oily the six pesticides named in the Interim Primary Drinking
Water Regulations are included: Endrin, Lindane, Methoxychlor,
Toxaphene; 2,4-D; and 2,4;5-TP (Silvex). Federal Register,
Vol. 40, No. 248, pp. 59570-59571, Dec. 24, 1975.
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" APPENDIX 16
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PERFORMANCE TESTS FOR THE EVALUATION
OF COMPUTERIZED
GAS CHROMATOGRAPHY/MASS SPECTROMETRY
EQUIPMENT AND LABORATORIES
by
William L. Budde
I - and
James W. Eichelberger
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1 Environmental Monitoring and Support Laboratory
Office of Research and Development
U.S. Environmental Protection Agency
Cincinnati, Ohio 45268
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...... ____ ._ ...... _______________ I
I
;"" "" ...... DISCLAIMER "~ ..... ~" "
This report has been reviewed by the Environmental Monitoring and
Support Laboratory, U.S. Environmental Protection Agency, and approved for
publication. Mention of trade names or commercial products does not
constitute endorsement or recommendation for use. I
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FOREWORD -
Environmental measurements are required to determine the quality of
ambient waters and the character of waste effluents. The Environmental
Monitoring and Support Laboratory - Cincinnati, conducts research to:
+ Develop and evaluate methods to measure the presence and concentra-
tion of physical, chemical, and radiological pollutants in water,
wastewater, bottom sediments, and solid waste.
* Investigate methods for the concentration, recovery, and identifica-
tion of viruses, bacteria and other microbiological organisms in
water; and, to determine the responses of aquatic organisms to water
quality.
+ Develop and operate an Agency-wide quality assurance program to assure
standardization and quality control of systems for monitoring water
and wastewater.
+ Develop and operate a computerized system for instrument automation
leading to improved data collection, analysis, and quality control.
This report was developed by the Advanced Instrumentation Section of the
Environmental Monitoring and Support Laboratory. It describes a series of
general purpose tests to evaluate the performance of computerized gas
chromatography-mass spectrometry (6C/MS) systems. Some of the tests go
beyond equipment performance and may be used to evaluate the performance of
laboratories using GC/MS for organics analysis. The report will be useful
to the many Federal, State, local government, and private laboratories that
are planning to employ this powerful analytical tool.
Dwight S. Ballinger
Director
Environmental Monitoring and Support
Laboratory - Cincinnati
111
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ABSTRACT
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A series of ten general purpose tests are described which are used to |
evaluate the performance of computerized gas chromatography-mass
spectrometry systems. Evaluation criteria are given with each performance
test. Some of the tests go beyond equipment performance, and may be used to
evaluate the performance of laboratories using 6S/MS for organics analysis.
tv
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CONTEHTS
Foreword i 1 i
Abstract iv
Figures vi
Tables v1
Acknow 1 edgment vi 1
1. Introduction 1
2. Summary of Tests .3
3. Experimental Procedures 5
Test I Spectrum Validation 5
Test II System Stability 8
Test III Instrument Detection Limit 8
Test IV Saturation Recovery 11
Test V Precision 12
Test VI Library Search 36
Test VII Quantitative Analysis with Liquid-Liquid Extraction 17
Test VIII Quantitative Analysis with Inert Gas Purge and Trap 19
Test IX Qualitative Analysis with Real Samples 27
Test X Solid Probe Inlet System 30
4. References 32
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FIGURES . I
Number Page
1 Control chart for nitrobenzene In clean water 21
Control chart for pyrene 1n clean water 22 I
2
TABLES |
Number _ _ _ . _ _. Page
1 Suggested GC Columns and Conditions 7 |
2 Decafluorotrlphenylphosphine Key Ions and Ion Abundance 7 _
Criteria |
3 Ions Over 3* Relative Abundance Observed in the 70 ev Mass
Spectrum of DFTPP 10
4 Common Background Ions in GC/MS Systems 11 »
5 Precision Statistics for Ten Priority Pollutants Plus |
Octadecane 13
6 Precision Statistics Using an Internal Standard 15 I
7 p_-8romofluorofaenzene Key Ions and Ion Abundance Criteria 16
8 Precision and Accuracy Data for Liquid-Liquid Extraction I
with GC/MS and an External Standard 20
9 Method Efficiencies for Some Priority Pollutants Plus
p_-Bromofluorobenzene 25
10 Precision and Accuracy Data for the Purge and Trap Analysis
with GC/MS and an External Standard 26
11 Precision and Accuracy Data for the Purge and Trap Analysis I
with GC/MS and the Internal Standard p_-Bromof luorobenzene 28
12 Precision and Accuracy Data for the Purge and Trap Analysis
with GC/MS and the Internal Standard Dibromochloromethane 29
vi
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^x._
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ACKNOWLEDGMENT
The authors wish to acknowledge the careful and competent technical
assistance of William Middleton, Jr., who has performed all of the GC/MS
tests described in this report at least once, and several of them hundreds
of times.
A number of Environmental Protection Agency personnel reviewed the first
draft of this report, and many provided written comments which substantially
assisted the authors in the preparation of this document. Our deep
appreciation is due to all of the following:
William Andrade
Region 1
Surveillance and Analysis Division
Lexington, MA 02173
Thomas A. Beliar
Environmental Monitoring and
Support Laboratory
Cincinnati, OH 45268
Robert L. Booth, Deputy Director
Environmental Monitoring and
Support Laboratory
Cincinnati, OH 45268
Aubry E. Dupuy, Jr.
Pesticides Monitoring Laboratory
Bay Saint Louis, MS 39520
Robert D. Kleopfer
Region 7
Surveillance and Analysis Division
Kansas City, KS 66115
John Logsdon
National Enforcement
Investigation Center
Denver, CO 80225
Dwight G. Ballinger, Director
Environmental Monitoring and
Support Laboratory
Cincinnati, OH 45268
Joseph N. Blazevich
Region 10
Surveillance and Analysis Division
Manchester, WA 98353
Herbert J. Brass
Division of Technical Support
Cincinnati, OH 45268
Denis Foerst
Environmental Monitoring and
Support Laboratory
Cincinnati, OH 45268
John Kopp
Environmental Monitoring and
Support Laboratory
Cincinnati, OH 45268
E. William Loy, Jr.
Region 4
Surveillance and Analysis Division
Athens, GA 30601
vii
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John M. McGuire
Environmental Research Laboratory
Athens, GA 30601
Aaron A. Rosen
Cincinnati Water Works
Cincinnati, OH 45228
0. C. Shew
R. S. Kerr Environmental
Research Laboratory
Ada, OK 74820
*
Alan Stevens
Municipal Environmental
Research Laboratory
Cincinnati, OH 45268
Curt Norwood
Environmental Research Laboratory
Narragansett, RI 02882
Dennis R. Seeger
Municipal Environmental
Research Laboratory
Cincinnati, OH 45268
Clois Slocum
Municipal Environmental Research
Laboratory
Cincinnati, OH 45268
Emilio Sturino
Region 5
Surveillance and Analysis Division
Chicago, IL 60606
v11t
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SECTION 1
INTRODUCTION
This report gives a series of performance tests to evaluate computerized
gas chromatography - mass spectrometry (GC/MS) systems. These tests were
designed for general use, and are applicable to all types of GC/MS systems.
All of the tests use the continuous, repetitive measurement of spectra
method of data acquisition, and no selected ion monitoring tests are
included. Except for the spectrum validation test (Test I), these
performance tests are not intended for routine application in a quality
assurance program. Test I is a required daily quality control test for
GC/MS systems in routine use for measurements of organic compounds in
environmental samples. The other performance tests are intended for use in
the evaluation of new GC/MS systems before purchase, or after the completion
of the manufacturer's installation. These tests are also useful to evaluate
GC/MS performance after a long period of downtime for extensive maintenance
or repair, after a long period of equipment neglect or non-use, or as
gene'ral training experiments for GC/MS operators. Several of the tests go
beyond equipment performance and may be used to evaluate the performance of
laboratories using GC/MS for organics analysis.
The performance tests described in this report are more rigorous and
extensive than the typical manufacturer's installation tests. Indeed, this
was intended, and the emphasis of the tests is on an evaluation of the total
operating system in a rigorous way using experiments that closely resemble
real, day-to-day operating situations. The performance tests should be
conducted in the order given, but several are optional or depend on the
availability of certain accessories, e.g., the solid probe inlet test.
All the tests described in this report require an operator, and some
depend heavily on the skills of laboratory personnel. Therefore, the
results of some tests may be limited by the skills available in the
laboratory. An experienced, two-person team consisting of a professional
scientist and a technician will require approximately three weeks to
complete the equipment tests assuming there are no major hardware or
software problems. Inexperienced teams or individuals may require anywhere
from six weeks to one year to complete all the tests, especially if major
hardware or software problems develop. In these tests, the operator and
other laboratory personnel are a crucial part of the total operating system.
The examples given in this report reference packed column gas chromatog-
raphy, but the tests described are equally applicable to open tubular GC/MS
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systems. With open tubular (capillary) systems some minor adjustments in
operating conditions may be necessary. |
For all the tests 1t Is assumed that the manufacturer has provided
acceptable documentation of users instructions for the operation and |
maintenance of the GC/MS system. At the very minimum this must include
clearly written descriptions of all operating and test functions, clear _
descriptions of all commands used in the operation of the data system,
examples of all commands, and intelligible documentation of error messages.
Examples of all outputs must be included as well as error recovery
procedures. There must be a narrative description of all data system files,
and the narrative should describe the exact nature of the algorithm used for
all the significant mass spectrometric processes. The maintenance manuals
must include a complete set of hardware engineering drawings, and
maintenance must be described 1n terms of block diagrams, logic diagrams, |
flow charts, circuit descriptions, and parts lists.
It is also assumed that the laboratory has provided the GC/MS facility I
with an appropriate environment including air conditioning and other
utilities as required, trained management and operating personnel, needed
supplies, essential support equipment, and a reasonable amount of working
space which allows access at the sides and rear of the system for
maintenance.
Finally, a system logbook must be maintained throughout the evaluation J
period. This must include an entry for every working day noting the status
of the system. This entry must be made even if the system is not used on _
that day, and signed by the responsible person. The logbook must include a
complete record of the number of gas chromatographic injections per day, the *
number of solid probe samples, all chromatographic column changes, all
maintenance procedures, ^all^ requirements for service from the manufacturer,
and each entry must be^sigrfed -and dated. This information must be
summarized in the performance evaluation report, and the mean numbers of gas
chromatographic injections and solid probe samples before ion source
maintenance (cleaning) must be reported.
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SECTION 2
SUMMARY OF PERFORMANCE TESTS
I. Spectrum Validation Test - Uses decafluorotriphenyl phosphine (DFTPP)
to determine whether the system gives a 70 ev electron ionizatlon
fragmentation pattern similar to that found in the historical mass
spectrometry data base, and the required mass resolution and natural
abundance isotope patterns. The spectrum of DFTPP must meet the
criteria given in Table 2.
II. System Stability Test - Uses DFTPP to test moderate term (20-28 hours)
system stability. The criteria given in Test I must be met.
III. Instrument Detection Limit Test - Uses DFTPP to measure the full and
valid spectrum detection limit at a defined and tolerable noise
level. At a signal/noise a 5, the required instrument detection
limits are 50 nanograms for systems used in the analysis of industrial
or municipal wastes, and 30 nanograms for systems used in the analysis
for ambient or drinking water.
IV. Saturation Recovery Test - Uses DFTPP and jp-bromobiphenyl to simulate
a frequently encountered situation with real samples. The spectrum of
DFTPP, measured'"within two minutes after the elution of a 250 fold
excess of p_-bromobiphenyl, must not contain significant contributions
from the ions attributable to £-bromobiphenyl.
V. Precision Test - Uses a variety of typical environmental pollutants to
determine precision from filling a syringe to peak integration. The
mean relative standard deviation for the compounds used in the test
which elute as narrow peaks must be 7% or less using either peak areas
in arbitrary units or ratios of peak areas. For broad peaks the mean
relative standard deviation must be 13% or less.
VI. Library Search Test - Uses data from Test V to evaluate the speed and
completeness of the minicomputer library search algorithm. The mean
search time, including background subtraction, must be one minute or
less, and all test compounds must be identified as most probable
except isomers with very similar spectra should not be counted as
incorrect.
VII. Quantitative Analysis with Liquid-Liquid Extraction -.Uses a variety
of environmental pollutants to measure quantitative SUcuracy and
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range of 90-110% with a mean relative standard deviation of 19% or
less using either internal or external standards.
I
precision of the total analytical method. The mean of the means of
the percentages of the true values observed must be in the 68-132*
range with a mean relative standard deviation of 38% or less using
either internal or external standards. This test also evaluates
laboratory performance.
I
VIII. Quantitative Analysis with Inert Gas Purge and Trap - Uses a variety
of compounds to measure quantitative accuracy and precision of the .
total analytical method. The mean of the mean method efficiencies m
must be 70% or more. Chloroform efficiency must exceed 90% and all
compounds must exceed 30* efficiency. The spectrum of £-bromofluoro-
benzene must meet the criteria given in Table 7. The mean of the I
means of the percentages of the true values observed must be in the
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IX. Qualitative Analysis with Real Samples - Uses a real sample to ' m
evaluate the ability of the system to deal with real sample matrix I
effects and interferences. All compounds must be correctly identified
except isomers with nearly identical mass spectra should not be
counted as incorrect. This test also evaluates laboratory performance.
X. Solid Probe Inlet System Test (Optional) - Uses cholesterol to
evaluate the spectrum validity achievable with a solid probe inlet
system. The spectrum of cholesterol must meet the criteria given in J
step three of the test.
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SECTION 3
EXPERIMENTAL PROCEDURES
I. Spectrum Validation Test
Correct identifications of organic pollutants from gas chromatography
mass spectrometry (GC/MS) data require valid mass spectra of the compounds
detected. This is prerequisite to the interpretation of the spectra, i.e.,
either an empirical search for a match within a collection of authentic
spectra or an analysis from the principles of organic ion fragmentation. A
properly operating and well tuned GC/MS is required to obtain valid mass
spectra.
The purpose of this test is to make a quick check - about 15 minutes -
of the performance of the total operating system of a computerized GC/MS.
Thus with a minimum expenditure of time, an operator can be reasonably sure
that the GC column, the enrichment device, the ion source, the ion separa-
ting device, the ion detection device, the signal amplifying circuits, the
analog to digital converter, the data reduction system, and the data output
system are all functioning properly.
An unsuccessful test requires, of course, the examination of the
individual subsystems and correction of the faulty component. Environmental
data acquired after a successful systems check are, in a real sense, vali-
dated and of far more value than unvalidated data. Environmental data
acquired after an unsuccessful test may be worthless and may cause erroneous
identifications.
It is recommended that the test be applied at the beginning of a work
day on which the system will be used and also anytime there is a suspicion
of a malfunction. A mass spectrometer which meets the criteria of this test
will, in general, generate mass spectra of organic compounds which are very
similar, if not identical, to spectra in collections and textbooks which
have been developed over the years with other types of spectrometers. If
the performance criteria of this test cannot be met by the user, the system
is unacceptable for general purpose environmental measurements.
Procedure:
1. Make up a stock solution of decafluorotriphenylphosphine (DFTPP)
at one milligram per mi Hi liter (1000 ppm) concentration in
acetone (or a hydrocarbon solvent). The reference compound used
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in this test is available from PCR, Inc., P. 0. Box 1778, _
Gainesville, Florida, 32602 and may be named bis (perfluorophenyl)
phenylphosphine. This stock solution was shown to be 97+% stable
after six months and indications are that it will remain usable
for several years. Dilute an aliquot of the stock solution to 10
micrograms per milliliter (10 ppm) concentration in acetone. The
very small quantity of material present in very dilute solutions
1s subject to depreciation due to adsorption on the walls of the
glass container, reaction with trace impurities in acetone, etc. |
Therefore, this solution will be usable only in the short term,
perhaps one week. _
2. Select a GC column for the tests. Any column that elutes OFTPP in
a reasonable time may be used, and several suggested columns are
listed in Table 1. Parameters should be adjusted to permit at
least four mass scans during elution of the DFTPP. This will
permit selection of a spectrum that is reasonably free of
abundance distortions due to rapidly changing sample pressure.
3. Set the preamplifier to a suitable sensitivity, set the baseline
threshold (zero instrument), and calibrate. m
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4. Prepare for data acquisition with the following variables: m
Mass Range: 40-450 amu
Scan Time: approximately five seconds m
Electron Energy: 70 ev
Electron Multiplier: Not to exceed that recommended by the
supplier for the age of the device. |
5. Inject with a syringe 50 nanograms (five micro!iters) of the B
dilute standard into the GC column.
6. After the acetone elutes from the column and is pumped or diverted
from the system, turn on the ionizer and start scanning.
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7. Terminate the run after the DFTPP elutes, turn the ionizer and
multiplier off, and plot the total ion current profile.
8. Select a spectrum number on the front side of the GC peak as near
the apex as possible, select a background spectrum number _
immediately preceding the peak, and display the background
subtracted spectrum. Some data systems permit spectrum averaging
to minimize variations 1n ion abundance due to rapidly changing
sample pressure. This option is acceptable, and may be required
for narrow peaks from open tubular columns. I
9. The mass spectrum can be output in various ways including a plot
of the full spectrum on the plotter or cathode ray tube or a print |
of the full spectrum on a printer or cathode ray tube.
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TABLE 1. SUGGESTED GC COLUMNS AND CONDITIONS
Dimension (Type) Packing Flow Rate Temp. R. Time
2m x 2 mm ID 1.95% QF-1 plus 30 ml/min 180 4 min
(Glass) 1.5% OV-17 on
80/100 mesh Gas-Chrom Q
2m x 2 mm ID 3% OV-1 on 80/100 30 ml/min 220 5 min
(Glass) mesh Chromosorb W
2m x 2 mm ID 5% OV-17 on 80/100 30 ral/m1n 220 5 rain
mesh Chromosorb W
2m x 2 mm ID 1% SP2250 on 100/120 30 ml/min 170 5 min
(Glass) mesh Supelcoport
30m x .25mm ID Wall coated SP 2100 2-5 ml/min 40,240 10 min
(Glass)
The spectrum obtained on the test system must contain ion abundances within
limits given for the key ions in Table 2 (1).
If the relative abundances are not within the limits specified, the
appropriate adjustments must be made, I.e., resolution, source potentials,
calibration of the mass scale, source magnet position, etc. The manufac-
turer may need to be consulted for assistance in this adjustment. Repeat
this test until satisfactory results are obtained.
TABLE 2. DECAFLUOROTRIPHENYLPHOSPHINE KEY IONS AND ION ABUNDANCE CRITERIA.-
Mass Ion Abundance Criteria
51 30-80% of Mass 198
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1
68 - Less than 2% of Mass 69
70 Less than 2% of Mass 69
127 30-70% of Mass 198
197 Less than 1% of Mass 198
198 Base Peak, 100% Relative Abundance
199 5-9% of Mass 198
275 10-30% of Mass 198
365 At least 1% of Mass 198
441 Present, but less than Mass 443
442 Greater than 40% of Mass 198
443 17-23% of Mass 442
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I ^-Criteria for masses 51 and 127 are modifications of previous values (1)
based on new inter laboratory data.
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II. System Stability Test -
The purpose of this test is to evaluate moderate term system stability.
Repeat the test described in Section I after 20-28 hours. Do not make any
adjustments or recalibration of the system between tests except routine
overnight procedures. The abundance criteria in Table 2 must be met. If I
these criteria are not met, the system is too unstable for routine use and
must be repaired.
III. Instrument Detection Limit Test
This test is to determine the smallest quantity of standard test I
material that can be injected into the GC/MS system that gives an acceptable *
spectrum meeting the criteria in Table 2, but has a sufficiently low level
of background signals to allow correct interpretation of that spectrum if
the sample was an unknown. A spectrum of a test compound contaminated with I
background signals to the extent of about 10X or more of Its total ion
abundance is considered to be difficult or impossible to interpret
correctly. This judgment is somewhat variable because 102 background dis- |
tributed among a large number of small ions may be acceptable, but a
distribution among a few large ions will be unacceptable. Therefore, a
signal to noise ratio based on a selection of six ions is used to evaluate
the detection limit. This also allows a relatively simple calculation of
the ratio.
In a GC/MS system there are a number of potential sources of background
signals (chemical noise) including septum bleed, stationary phase bleed,
vacuum system background from various physical components, and ion source
contamin- ation. Furthermore, all signals are dependent on GC" column |
efficiency, enrichment device efficiency, vacuum system efficiency, ioniza-
tion efficiency, ion transmission efficiency, and detector gain. Therefore,
this test is highly sensitive to the specific system.configuration (specific
GC column, etc.; and the current condition of that system, e.g., condition *
of the GC column, extent of contamination in the ion source, extent of
contamination of the quadrupole rods if a quadrupole instrument, and
condition of the electron multiplier. The state of the system should be I
documented as part of the records of the instrument detection limit test.
Procedure: , g
1. Make three dilutions of the stock solution of DFTPP described in Test
I. The dilutions should have the concentrations of five micrograms
per milliliter, one microgram per milliliter, and one-tenth of a *
microgram per milliliter.
2. Follow the basic procedures given in Test I and make the following I
series of injections:
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Amount Injected Volumes and Standards
20 nanograms 4 ul of 5 ug/ml standard
10 nanograms 2 ul of 5 ug/ml standard
5 nanograms 1 ul of 5 ug/ml standard
1 nanogram 1 ul of 1 ug/ml standard
100 picograms 1 ul of 0.1 ug/ml standard
3. List the masses, relative abundances, and/or absolute abundances
(intensities) of the background subtracted spectra of DFTPP. Sub-
tract the background spectra as described in Test I. If necessary
use an extracted ion current profile to locate the GC peak. Discard
all spectra that do not meet the criteria in Table 2. From the
remaining spectra discard those that do not display at least six
non-OFTPP ions with relative abundances greater than 5%. If
additional dilutions or measurements are necessary, do them. Table 3
contains all DFTPP ions over 3% relative abundance and Table 4
contains a group of common background ions.
4. For each of the qualified spectra compute the ratio R as follows:
Lf DFTPP)
[BACKGD)
where:
(DFTPP) « the summation of the abundances of the ions at
masses 127, 255, 275, 441, 442 and 443
(BACKGD) « the summation of the abundances of the six most
abundant (but each over 5% relative abundance) non-OFTPP
background ions
Prepare a plot of R values as a function of amount injected. The
instrument detection limit defined in this test is for the complete,
valid spectrum with a defined level of acceptable noise. This
detection limit is the amount injected that gives an R value of
five. If sufficient points are available, a good estimate of the
instrument detection limit may be obtained from a first or second
order regression on this data.
The rationale for the selection of an R value of five is consistent
with the previous statement that background ions should be less than
about 10% of the total ion abundance in an interpretable spectrum.
The average relative abundance of the six DFTPP ions used to compute
R is in the 25-35% range. For an R value of five the average
relative abundance of the six background ions will be in the 5-7%
range, and it is estimated that all background ions under these
conditions will be less than 10% of the total ion abundance.
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TABLE 3. IONS OVER 3% RELATIVE ABUNDANCE OBSERVED
' IN THE 70 ev MASS SPECTRUM OF DFTPP |
AMU . INTENSITY PERCENT OF TOTAL INTENSITY I
50.0 8.11 1.11
51.0 34.60 4.74
69.0 32.93 4.51 I
74.0 3.10 0.42
75.0 4.53 0.62
77.0 34.84 4.77 I
78.0 3.10 0.42
93.0 3.10 0.42 _
99.0 3.81 0.52 I
107.0 10.97 1.50
110.0 20.76 2.84
117.0 6.44 0.88
127.0 37.70 5.16 1
128.0 - - . - - 3.10 - 0.42
129.0 12.88 1.76
167.0 4.05 0.55
168.0 4.77 0.65
186.0 13.12 1.79 _
187.0 3.81 0.52 I
198.0 100.00 13.69
199.0 7.15 0.98
205.0 5.01 0.68
206.0 20.28 2.77 I
207.0 - 4.53 0.62
217.0 5.01 0.68 .
221.0 4.29 0.58 I
224.0 11.21 1.53 "
227.0 3.81 0.52
244.0 8.11 1.11 I
255.0 49.16 6.73
256.0 7.39 1.01
274.0 4.29 0.58
275.0 23.15 3.17 I
276.0 3.81 0.52
296.0 5.01 0.68 m
423.0 3.34 0.45 I
441.0 9.30 1.27 "
442.0 69.45 9.51
443.0 12.88 1.76 I
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TABLE 4. COMMON BACKGROUND IONS IN GC/MS SYSTEMS
Masses Sources
41,43,55,57, Saturated hydrocarbons and
69,71,81,83, unsaturated hydrocarbons -
85,95,97,99 cyclic and open chain-many sources
149 Phthalate esters used as plasticizers
in tubing, etc.
73,101,135,197,207 Methyl and phenyl silicone
259,345,346,355 polymers used in stationary
phases, diffusion pump oil, etc.
169,251 Polyphenyl ether diffusion
pump oil
The required instrument detection limits, at an R value of five, are 50
nanograms for systems used in the analyses of industrial or municipal
wastes, and 30 nanograms for systems used in analyses of ambient or drinking
waters. These limits were obtained from considerations of EPA recommended
sample sizes and concentration factors. If a system cannot meet these
criteria, maintenance or repair is required. Particular attention should be
given to those items mentioned in the second paragraph of this test.
Observed detection limits with this test are as follows:
1. A Finnigan 3200 equipped with a Varian 1400 GC, a packed 1% SP 2250
Column (Table 1), a Systems Industries RIB interface, and a POP-8
datasystem (disk) gave a detection limit of five nanograms.
2. A Finnigan 4000 with a Finnigan 9610 GC, a packed 1% SP 2250 column
(Table 1), an INCOS interface, and an INCOS datasystem (Nova 3, disk)
gave a detection limit of 25 nanograms.
IV. Saturation Recovery Test
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The purpose of this test is to evaluate the ability of a system to
measure the spectrum of a test compound at a low level immediately after a
relatively large quantity of another compound entered the system. This
situation occurs frequently in real environmental samples, especially waste
samples where a very large concentration of one component may saturate the
detector, and within a few minutes or less a very small quantity of a
compound of interest may enter the detector.
Procedure:
1. Prepare an acetone solution containing five milligrams per mi Hi liter
of £-bromobiphenyl and 20 micrograms per mi Hi liter £f DFTPP. A
second solution containing approximately 50 micrograms per milliliter
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of each is optional and may be useful to optimi2e chromatographic
conditions. I
2. Establish GC conditions such that the DFTPP elutes within two minutes
after the elution of the £-bromobiphenyl. These conditions were |
achieved with a 6' x 2 mm 10 glass column packed with 1% SP2250 on
Supelcoport (100/120 mesh) using a flow of 30 ml of helium per minute
with the initial column temperature at 120°C and programming to I
230°C at 10° per minute. The £-bromobiphenyl eluted at 110
seconds and the DFTPP at 210 seconds. This test is carried out using
the same basic operating parameters given in Test I.
3. Inject two microliters of the standard solution containing the 250:1
ratio of p-bromobiphenyl to DFTPP. Plot the DFTPP spectrum as in
Test I. Each of the ions at masses 152, 232, and 234, which are the
three most abundant in the spectrum of £-bromob1phenyl, must be below
5% relative abundance in the background subtracted spectrum of DFTPP.
V. Precision Test
The purpose of this test is to measure the precision of the GC/MS system
in quantitative analysis using continuous, repetitive measurement of spectra. I
This test evaluates precision from filling a syringe to integration of the
peak area for a specific quantitation ion. The entire test should be
carried out on the same day by the same technician. The application of an
automatic sample changer in this test is required if it will be used for
normal sample, processing. This should be documented in the test results.
If acceptable precision cannot be obtained with this test, the precision of
a complete anaytical method may also be unacceptable.
*
Procedure:
*
1. Select a group of seven or more compounds, and prepare a standard
solution in acetone that contains the entire group. Some recommended «
compounds are in Table 5, and the concentration of each should be 20
micrograms per mi Hi liter. This group of compounds must include a
chlorinated hydrocarbon that may decompose on a hot metal surface and
a polycyclic aromatic hydrocarbon with a molecular weight greater
than 200. For compounds amenable to the inert gas purge and trap *
procedure, prepare the standard solution in methanol at the same
concentration. The purge and trap mixture must include chloroform,
bromoform, .syjn-tetrachloroethane, and p-bromofluorobenzene. Some |
recommended compounds are 1n Tables 9-12. This test may be conducted
with either or both groups of compounds.
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TABLE 5. PRECISION STATISTICS FOR TEN PRIORITY POLLUTANTS PLUS OCTAOECANE
COMPOUND
1,3-OICHLOROBENZENE
NAPHTHALENE
1,2,4-TRICHLOROBENZENE
£-OCTADECANE
DIMETHYL PHTHALATE
DI-ji-BUTYL PHTHALATE
N-NITROSOOIPHENYLAMINE
HEXACHLOROBENZENE
PYRENE
CHRYSENE
BENZO(A)PYRENE
INTEGRATION
MASS
146
128
ISO
254
163
149
169
284
202
228
252
PEAK*
TYPE
N
N
N
N
N
N
N
N
N
B
B
MEAN (S/MEAN AREA)
AREA S *100
6771 278 4.1
18077 375 2.1
5412 195 3.6
345 15 4.2
13540 501 3.7
21770 364 1.7
6460 228 3.5
4027 139 3.4
18107 607 3,4
10345 636 6.2
9518 681 7.2
* narrow; B * broad (see text for definitions)
2. Select an appropriate GC column. For compounds similar to those in
Table 5, the columns in Table 1 are satisfactory. For compounds,
amenable to purge and trap procedures, two acceptable columns are an
8 ft. stainless steel or glass column packed with 1% SP-1000 coated
on 60/80 mesh Carbopack B or packed with 0.2% Carbowax 1500 coated
on 60/80 mesh Carbopack C. Prepare for data acquisition with the
following variables:
mass range: 35-350 amu (For purge and trap compounds use 20-260 amu)
scan time: approximately six seconds (two or three seconds with open
tubular columns)
electron energy: 70 ev
electron multiplier: not to exceed that recommended by the
supplier for the age of the device.
3. Inject with a syringe or automatic sample changer four microliters
(80 nanograms of each compound) of the standard sol«$ion and acquire
data until all compounds have eluted from the column. Save the data
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file on the data system and repeat the injection a minimum of four
times, saving the data files 1n each case. I
4. Plot the total ion current profiles, and use a quantitation program
to integrate peak areas in arbitrary units (usually
analog-to-digital counts) over a specific quantitation mass for each |
compound In each data file. Precision may be evaluated using either
the peak areas in arbitrary units or ratios of peak areas. The
former gives a precision representative of external standardization,
and the latter a precision representative of internal
standardization. There will be no significant difference 1n the
results using the two methods 1f the system 1s operating properly
and acceptable syringe filling and injection techniques are used.
It is recommended that calculations be carried out using both
methods for comparison of results, but the minimum requirement 1s
that precision be evaluated using the method that corresponds to the |
standardization procedure used in the laboratory for environmental
samples. m
Table 5 1s an example of data from five replicate syringe injections
of 80 nanagrams of each compound using a Finnigan 3200 and a POP-8
based data system. The mean areas are in analog-to-digital I
converter units and the standard deviations (S) were'computed using
the equation below. The last column in Table 5 1s the relative
standard deviation which is (S/mean area)* 100. Table 6 contains
the results of computations with exactly the same raw data as in |
Table 5, but using ratios of areas as in Internal standard
calibrations. The response factor (RF) is defined "in test VII, and m
the mean response factors are shown in Table 6. The compound
di-n-butylphthalate was selected as the internal standard because 1t m
showed the smallest variation 1n peak area (1.7%, Table 5) and
eluted near the mid-point in the chromatogram. The standard I
deviations and relative standard deviations were computed as in
Table 5.
N * _ (JL - ~ 1
S » ",r, ca 1
.
N (N-l)
where:
S * the standard deviation
N * the number of measurements
for each compound
Area = the integrated 1on abundance of the
quantitation mass
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The compounds designated as having narrow peak types in Tables 5 and 6
had widths at half height of 45 seconds or less. The mean relative standard
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TABLE 6. PRECISION STATISTICS USING AN INTERNAL STANDARD
COMPOUND
1,3-DICHLOROBENZENE
NAPHTHALENE
1,2,4-TRICHLOROBENZENE
J1-OCTAOECANE
DIMETHYL PHTHALATE
DI-£-8UTYL PHTHALATE
N-NITROSODIPHENYLAMINE
HEXACHLOROBENZENE
PYRENE
CHRYSENE
BENZO(A)PYRENE
INTEGRATION PEAK1
MASS TYPE
146
128
180 -'
254
163
149
169
284
202
228
252
N
N
N
N
N
N
N
N
N
B
B
MEAN
RF
0.3112
0.83048
0.2486
0.0158
0.62202
1.00000
0.2968
0.1850
0.83171
0.4751
0.4370
(S/MEAN RF)
S *100
0.01512
0.017250
0.008571
0.000838
0.022980
0.00000
0.01008
0.005899
0.023110
0.02619
JO. 0275
4.9
2.1
3.4
5.3
3.7
0
3.4
3.2
2.8
5.5
6.3
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deviation for the data in Table 5 1s 3.32, and the corresponding mean from
Table 6 is 3.6 2. Therefore there was no significant difference in the I
precision of external and internal standardization. The requirement of this
test is that the mean relative standard deviation of data from narrow peaks
be 7% or less. This requirement is based on the general observation that
data from interlaboratory comparisons is usually about a factor of two more |
variable than single laboratory data, and this 1s a reasonable requirement
for an acceptable system. _
The last two compounds 1n Tables 5 and 6 gave broader peaks with peak B
widths at half height of more than 45 seconds. Measurements of these are
more variable because of the changing baseline during temperature
programming and other factors, pie mean relative standard deviations from
Tables 5 and 6 are 6.72 and 5.^'respectively, and internal standardization
may have some slight advantage for these peaks but there are too few data
points to judge the significance of this. The requirement of this test is |
that the mean relative standard deviation of data from broad peaks be 132 or
less. Again the rule of thumb on interlaboratory data was used to establish _
this requirement. I
If this test is conducted with compounds amenable to the Inert gas purge
and trap procedure, the compound £-bromofluorobenzene must be included in
the mixture. This compound is a secondary spectrum validation compound
which is used with GC columns that do not elute DFTPP. Therefore, after a
purge and trap column is installed for this test p_-bromofluorobenzene may be
used as a daily check on spectrum validity. The ion abundance criteria for |
p_-bromofluorobenzene are 1n Table 7, and these are consistent-with the OFTPP
criteria in Table 2. -
TABLE 7. £-BROMOFLUOROBENZENE KEY IONS AND ION ABUNDANCE CRITERIA
Mass ' Ion Abundance Criteria I
50 20-402 of the base peak
75 50-702 of the base peak
95 base peak, 1002 relative |
abundance
96 5-92 of the base peak _
173 less than 12 of the base peak
174 : greater than 502 of the base peak
175 5-92 of mass 174
176 greater than 502 of the base peak I
177 5-92 of mass 176
VI. Library Search Test
Minimum requirements for the library search are the availability of the
EPA/NIH database which Is distributed through the National Bureau of .
Standards. The searchable database may be a subset of the EPA/NIH database,
but the subset must contain at least 10,000 spectra of general and m
environmental interest and the Chemical Abstracts Service (CAS) registry
numbers for each compound. Programs must be available to allow the operator I
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to submit background corrected spectra to the library search, and receive a
printed report of the search results. The spectra from one of the
experiments in Test V should be submitted to the library search system.
Each compound must be identified as the most probable by the library search,
except isomers that may have very similar 70 ev El mass spectra should not
be counted as incorrect. The mean search time, including the time for
background subtraction, should be one minute or less. Printed reports
should include CAS numbers. During this test make several deliberate
typical operator errors, such as entry of an incorrect command and a
non-existent file name. The data system should respond with an intelligible
error message, and return to a logical continuation point.
VII. Quantitative Analysis with Liquid-Liquid Extraction
This test uses a variety of environmental pollutants to measure quanti-
tative accuracy and precision of the total analytical method, but without
the complications of real sample matrix effects. The test is designed for
laboratories that conduct quantitative analyses of water samples with GC/MS
using continuous repetitive measurement of spectra. Therefore, laboratories
dealing in other media should design a similar test based on some standard
reference material. The principal difference between this test and Test V,
the precision test, is the consideration of potential errors and variations
due to: (a) extraction of the compounds from a clean water matrix; (b)
concentration of the extract to a small volume; and (c) standardization of
the measured areas in terms of the concentration of the original sample in
micrograms per liter. This is one of the tests that goes beyond equipment
performance, and may be used to evaluate the performance of laboratories
using GC/MS for organics analysis.
It is recommended that the same standard solution of seven or more
compounds that may have been prepared for the precision test (Test V) be
used in this test since retention information is already available, and the
concentrations are in an acceptable range. However, new standards may be
used and the seven or more compounds should be at the 20 microgram per
mi Hi liter level in acetone.
Procedure:
1. Add 250 microljters (five micrograms of each compound) of the mixed
standard solution in acetone to each of a minimum of five liters of
clean water. This aqueous solution is called a laboratory control
standard. Set aside one additional liter of clean water as a
reagent blank.
2. Carry out the extractions according to the established procedures
(2,3,4). The methylene chloride extract must be concentrated to 0.5
milliliter. The blank should be measured first by itself, and if
significant contamination is found, correct the problems before
proceeding with this test. See the references cited above for
information on the interpretation of blanks.
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With an internal standard P 1s computed with the equation below
* which assumes the response factors are defined as above:
area (concentrated extracts) *100
area (external standard)
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p s area (concentrated extract) *100
area (internal standard) *RF
Table 8 shows precision and accuracy data obtained for eight compounds
extracted from clean water with methylene chloride and measured with GC/MS
using a single external standard. The GC/MS was a Finnigan model 3200 with
a PDP-8 based datasystem. One difference between the data in Table 8 and
the procedures described in this test is that the data in Table 8 represents
duplicate extractions and measurements at four different concentration
levels between 15-200 micrograms per liter for each compound. Figures 1 and
2 show control charts which contain all eight P values for each of two of
the compounds. This is a recommended method (5) of displaying precision and
accuracy data. Charts should be labelled as in Figures 1 and 2. General
experience shows that P values measured over a concentration range of one or
two orders of magnitude are often concentration independent within the
precision of the method.
The mean of the P values in Table 8 is 84%. Therefore, the requirement
of this test is that the mean of the mean P values of the compounds used in
this test must be in the range of 68-132%. Again, as in Test V, the
expectation is that multi-laboratory data will usually be about a factor of
two more variable than single laboratory data. The mean relative standard
deviation from Table 8 is 19%, and the requirement of this test is that the
mean relative standard deviation be 38% or less.
VIII. Quantitative Analysis with Inert Gas Purge and Trap
This test uses a variety of environmental pollutants to measure
quantitative accuracy and precision of the total analytical method, but
without the complications of real sample matrix effects. The test is
designed for laboratories that conduct quantitative analyses of water
samples with GC/MS using continuous repetitive measurement of spectra.
Therefore, laboratories dealing in other media should design a similar test
based on some standard reference material. The principal difference between
this test and Test V, the precision test, is the consideration of potential
errors and variations due to: (a) purging of the compounds from a clean
water matrix; (b) trapping and desorption of the compounds; and (c)
standardization of the measured areas in terms of the concentration of the
original sample in micrograms per liter. This test is required to evaluate
purge and trap equipment that is delivered as an integral part of a GC/MS
system, or other purge and trap equipment that is interfaced to the GC/MS
system.
The series of experiments in this test is used to generate three key
pieces of information about purge and trap performance:
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TABLE 8. PRECISION AND ACCURACY DATA FOR LIQUID-LIQUID EXTRACTION
WITH GC/MS AND AN EXTERNAL STANDARD |
INTEGRATION MEAN (S/MEAN P)
COMPOUND MASS P S *100 f
NITROBENZENE 123 94 8.8 9.4 -
1,2,3-TRICHLOROBENZENE 180 85 13 15
NAPHTHALENE 128 73 18 25 |
ACENAPHTHYLENE 152 83 15 18
N-NITROSODIPHENYLAMINE 169 89 19 21 |
FLUORANTHENE 202 80 19 24 _
PYRENE 202 83 19 23
n.-BUTYLBENZYLPHTHALATE 206 86 17 20 |
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1
1
1
1
1
1120
,
110-
100'
2i 90-
1 1 "
u
e 70'
60'
1
40-
1
1
1
Figure 1
1
1
r
Compound: nitrobenzene ' Data acquisition : 35 - 400amu
Range: 50 - 200ug/l Quantitation: mass 123. one
. , .. ,.u /», external standard
Method: extraction. CH2C12
Relative standard deviation: 9%
o
o
O O
0
o
8/31 8/31 8/31 8/31 9/5 9/5 9/5 9/5
Experiment Date (1978)
, Control chart for nitrobenzene in clean water.
21
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140
Compound: pyrene
Range: 15 130pg/l
Method: extraction. CH2C12
Relative standard deviation: 23%
Data acquisition: 35 - 400 amu
Quantitation: mass 202. one
external standard
130H
120'
no
i
100
£90<
I "~
, I 80.
I o
S S 70
' C
I 60
j 50
i
I 40
30
20
MEAN * 3S
MEAN + S
-MEAN = 83.4 (S-19)
MEAN - S
MEAN - 3S
8/31 8/31 8/31 8/31 9/5 9/5 9/5 9/5
Experiment Date (1978)
Figure 2. Control chart for pyrene 1n clean water.
22
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(a) Method efficiency for test compounds by comparison of the measured
quantity from syringe injection into the GC with the quantity
measured after purging, trapping, and desorption. Because of the
method of calibration used in the purge and trap procedure high
method efficiency as defined above is not necessary for acceptable
precision and accuracy. However, high method efficiency is required
for acceptable sensitivity, and low method efficiency will result in
unacceptable detection limits. Also in the case of real samples, a
low method efficiency combined with an unfavorable matrix effect
could render the method totally useless.
(b) Precision of the overall purge, trap, desorption, and 6C/MS analysis.
(c) Accuracy of the overall purge, trap, desorption, and GC/MS analysis
in terms of the percentage of the true value found in laboratory
control standards.
All the above information may be obtained from the same set of data. It
is recommended that the same standard solution of seven or more compounds
amenable to purge and trap that was recommended for the precision test (Test
V) be used in this test since retention information may be already
available, and concentrations are in an acceptable range. However, new
standards may be used, and the seven or more compounds should be at the 20
micrograms per milliliter level in methanol. The purge and trap mixture
must include chloroform, bromaform, s^m-tetrachloroethane and
£-bromofluorobenzene.
Procedure:
1. Select an appropriate column (see Test V) and prepare for data
acquisition using the GC/MS operating parameters given in Test V. .
2. Add five microliters (100 nanograms of each compound) of the mixed
standard in methanol to each of a minimum of five aliquots of low
organic water. Purge and trap samples may be 5 ml to 25 ml, but 5
ml is recommended for optimum method efficiency. This aqueous
solution is called a laboratory control standard.
3. Carry out the purge and trap according to the established procedures
(2,3,4) at ambient temperature. A low organic water blank should be
measured first and at occasional intervals to detect instrument
contamination. If significant contamination is found, correct the
problems before proceeding with this test. See references cited
above for information on the interpretation of blanks.
4. Purge, trap, desorb, and obtain GC/MS data from a minimum of five
laboratory control standards and save all the data files. At about
the midpoint of the purge and trap analyses, inject with a syringe
five microliters (100 nanograms of each compound) of the mixed
standard in methanol into the purge and trap GC column. Acquire
23
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GC/MS data using the same acquisition parameters used for purge and
trap analyses. I
5. Plot the total 1on current profiles, and use a quantltatlon program
to Integrate peak areas 1n arbitrary units (usually analog-to- |
digital converter counts) over a specific quantitation mass for each
compound in each data file.
6. Method efficiency must be evaluated by comparing the measured areas
from direct GC Injection with the corresponding areas from the
purge, trap, and desorption experiments. Internal standards cannot
be used because method efficiencies for various compounds are not
yet known, and comparable response factors cannot be computed for
direct injection and purge/trap/desorption.
Prepare a table similar to Table 9 which shows data obtained with a
Finnigan model 3200, a POP-8"data system, and a Tekmar model, LSC-1
purge and trap device with a 25 ml sample container. The equation
used to compute method efficiencies (E) is shown below. The minimum
requirement of this test is that the mean of the mean method
efficiencies of the compounds used in this test be 703J or more. The
chloroform efficiency must exceed 90X and all compounds must be I
recovered with at least 30% efficiency. Also the spectrum obtained
from p-bromofluorobenzene must meet the ion abundance criteria given
in Table 7. If these requirements cannot be met, the system is |
unacceptable for quantitative analyses and needs repair or
redesign. One critical method variable that may be optimized is the
purge gas flow rate. I
*
P area (after purge and trap)
* area (direct injection)
7. Precision and accuracy data may be obtained by choosing one of the
experiments in the purge and trap set as a standard, and computing |
the percentages of the true values (P) measured in the other
laboratory control standards. This is consistent with the standard _
method of calibration used with the purge and trap method. The I
experiment chosen as the standard may either be treated as an "
external standard, or may be used to compute response factors for an
internal standard calibration. Table 10 shows the data from the
method efficiency determination recomputed by Ignoring the direct I
injection result, and using one-of the purge and trap experiments as
an external standard. -The equation used to compute the percentages "
of the true values (P) is as follows: |
p « area (after purge and trap) *,QQ _
area (external standard)
The standard deviation of P and relative standard deviation were
computed as described in Test V. The mean of the P values in Ta
10 is 95% and the mean relative standard deviation is 9.4S. The
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TABLE 9. METHOD EFFICIENCIES FOR SOME PRIORITY POLLUTANTS
PLUS £-BROMOFLUOROBEN2ENE
COMPOUND
CHLOROFORM
CARBON TETRACHLORIDE
BROMOOICHLOROMETHANE
TRICHLOROETHYLENE
DIBROMOCHLOROMETHANE
BROMOFORM
TETRACHLOROETHYLENE
Sym-TETRACHLOROETHANE
£-BROMOFLUOROBENZENE
INTEGRATION MEAN AREA AREA DIRECT
MASS PURGE/TRAP INJECTION
83 2883 3001
117 2289 2314
83 2925 3280
130 1474 1653
129 1572 2343
173 1241 2788
166 1737 2102
83 1032 3071
174 1542 2200
.
25
MEAN METHOD
EFFICIENCY^)
96
99
89
89
67
45
83
34
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TABLE 10. PRECISION AND ACCURACY DATA FOR THE PURGE AND TRAP
ANALYSIS WITH GC/MS AND AN EXTERNAL STANDARD
INTEGRATION . MEAN (S/MEAN P)
COMPOUND MASS P S *100
CHLOROFORM 83 92 8.8 9.5
CARBON TETRACHLORIDE 117 97 7.9 8.2
BROMODICHLOROMETHANE 83 96 7.2 7.5
TRICHLOROETHYLENE 130 94 7.4 7.9
DIBROMOCHLOROMETHANE 129 98 4.4 4.5
8ROMOFORM 173 96 5.2 5.4
TETRACHLOROETHYLENE 166 96 14 14
S^-TETRACHLOROETHANE 83 100 14 14
£-BROMOFLUOROBENZENE 174 90 12 14
-
.-
.
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requirement of this test is that the mean of the mean P values of
the compounds used in this test must be in the range of 90-110%.
This is based on the genera] rule, described in Test V, that data
from inter laboratory comparisons is usually about a factor of two
more variable than single laboratory data. The mean relative
standard deviation must be 19% or less on the same basis.
The percentages of the true values (P) may also be computed by
selecting one compound in the test mixture as an internal standard,
and using one of the purge and trap experiments to establish
response factors as defined in Test VII. The percentages of the
true values (P) in the other laboratory control standards are
computed as follows (the terms have the same meaning defined in Test
VII):
0 _ area (x) * 100
area (s) *RF
Table 11 shows the method efficiency data recomputed with
£-bromofluorobenzene as the internal standard. Response factors were
established with the same purge and trap experiment that was used as an
external standard for the computations in Table 10. Table 12 shows the same
data recomputed with dibromochloromethane as an internal standard. Again,
response factors were established with the same purge and trap experiment
that was used as an external standard for the computations in Table 10.
The internal standard calculations reveal that the percentages of the
true values observed and the relative standard deviations are a function of
the internal standard selected. The compound £-bromofluorobenzene eluted
late in the chromatogram after temperature programming, and measurements of
it were more variable because of this and other factors. This is reflected
in the mean of the mean P values from Table 11 of 108% and the mean relative
standard deviation of 12%. The compound dibromochloromethane showed the
least variation in the external standard data (Table 10) and is an excellent
internal standard. The mean of the mean P values from Table 12 is 97% with
a mean relative standard deviation of 6.5%. This illustrates that care must
be exercised in the selection of an internal standard because of the
potentially significant impact on the observed precision and accuracy. The
individual P values may also be charted as in Figures 1 and 2 to provide a
graphic presentation of the data.
IX. Qualitative Analysis with Real Samples
The purpose of this test is to evaluate the ability of the SC/MS system,
laboratory, and sample preparation methods to deal with natural background,
interferences, and sample matrices found in real environmental samples. The
tsst is limited to qualitative analyses because of the unpredictable
quantitatvie effects of the sample matrix. This is one of the tests that
goes beyond equipment performance, and it may be used to evaluate the
performance of laboratories using GC/MS for organics analysis. The test is
designed for laboratories that conduct qualitative analyses of water samples
with GC/MS using continuous, repetitive measurement of spectra.
27
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TABLE 11. PRECISION AND ACCURACY DATA FOR THE PURGE AND TRAP
ANALYSIS WITH GC/MS AND THE INTERNAL STANDARD £-BROMOFLUOROBENZENE
INTEGRATION MEAN - (S/MEAN P)
COMPOUND MASS P S *100
CHLOROFORM 83 103 13 13
CARBON TETRACHLORIDE 117 108 12 11
BROMODICHLOROMETHANE 83 > 107 12 11
TRICHLOROETHYLENE 130 105 12 11
DIBROMOCHLOROMETHANE 129 110 11 10
BROMOFORM 173 108 12 11
TETRACHLOROETHYLENE 166 107 13 12
Sym-TETRACHLOROETHANE 83 112 19 17
£-BROMOFLUOROBENZENE 174 100 0 0
-
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TABLE 12. PRECISION AND
ANALYSIS WITH GC/MS AND THE
ACCURACY DATA FOR THE PURGE AND TRAP
INTERNAL STANDARD DIBROMOCHLOROMETHANE
1 INTEGRATION MEAN (S/MEAN P)
COMPOUND
1
CHLOROFORM
CARBON TETRACHLORIDE
BROMODICHLOROMETHANE
| TRICHLOROETHYLENE
DIBROMOCHLOROMETHANE
BROMOFORM
TETRACHLOROETHYLENE
Sym-TETRACHLOROETHANE
| 2-BROMOFLUOROBENZENE
1
1
1
1
1
1
1
1
MASS
83
117
83
130
129
173
166
83
174
P S *100
94 5.8 6.2
98 4.3 4.4
98 3.7 3.7
95 3.8 4.0
100 0 0
98 2.0 2.0
98 9.8 10
101 11 11
92 9.7 11
-
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Procedure:
1. Acquire appropriate quality control samples. These should be 1n |
sealed glass ampoules containing one to fifty organic compounds
dissolved in acetone, methanol, or some other miscible organic .
solvent. The concentration levels should be suitable for the I
preparation of aqueous samples in the 10-500 micrograms per liter
range by addition of 250 or fewer microliters of the organic
solution to 5 to 1000 milliliters of an environmental sample.
Instructions for the dilutions must be supplied with the samples,
but the identity of the compounds in the ampoules must be supplied
separately in sealed envelopes to the laboratory management.
Samples of this type are available from: |
John A. Winter, Chief
Quality Assurance Branch .
EMSL-Cincinnati
Environmental Protection Agency
Cincinnati, Ohio 45268 |
2. Obtain an environmental sample typical of the type normally analyzed
in the laboratory. Add the quality control samples to the
environmental samples according to the instructions provided, and 8
proceed with the analyses using the appropriate method, e.g., as in
Tests VII and VIII. -
3. Plot the total ion current profiles and identify all the compounds
using the mass spectra. All compounds must be correctly identified
except, as in the library search, isomers with nearly identical 8
70 ev electron ionization spectra should not be counted as incorrect.
X. Solid Probe Inlet System Test (optional)
The purpose of this test is to evaluate the critical thermal character-
istics of the solid probe inlet system, and to determine whether valid _
spectra are produced with this system. The test uses cholesterol which is I
sensitive to thermal effects. Data acquisition is by continuous repetitive *
measurement of spectra.
Procedure: -, 8
1. Prepare a standard solution of cholesterol in acetone at a concen-
tration of 250 micrograms per milliliter. Evaporate one microliter |
of this solution in the solid probe sample holder.
2. Use the data acquisition parameters given in Test I, and gradually I
heat the sample until the cholesterol pressure increases and spectra
may be measured.
3. Terminate data acquisition and plot a background subtracted spectrum 8
of cholesterol as described in Test I. Measure the abundances of
the ions at masses 386 and 368, and compute the 386/368 abundance
30
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ratio. This should be 3.0 or greater for an acceptable solid probe
inlet system. The ion abundance at mass 369 should be 26-34% of the
abundance at mass 386. Finally large ions above 30% relative
abundance should be at masses 41, 43, 55, 57, 67, 69, 71, 79, 81,
83, 91, 93, 95, 105, 107, 109, 119, 121, 133, 145, 147, 149, 159,
161, 213, 275, 301, and 386.
31
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SECTION 4
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REFERENCES
1. Eichelberger, J.W., L.E. Harris, and W.L. Budde, "Reference Compound to
Calibrate Ion Abundance Measurements In Gas Chromatography - Mass
Spectrometry Systems," Anal. Chera., 47_, 995 (1975).
2. Budde, W.L., and J.W. Eichelberger, "An EPA Manual for Organics Analysis
Using Gas Chromatography - Mass Spectrometry," EPA Report No. EPA .
600/8-79-006, March, 1979. |
3. Budde, W.L., and J.W. Eichelberger, "Organics Analysis Using GC/MS," Ann _
Arbor Science Publishers, Ann Arbor, Michigan, July 1979.
4. "Guidelines Establishing Test Procedures for the Analysis of
Pollutants," Federal Register .
5. "Handbook for Analytical Quality Control in Water and Wastewater
Laboratories,* EPA Report No. EPA-600/4-79-019, March, 1979, Chapter 6. |
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APPENDIX 17
LIFE CYCLE OF AN ON-SITE SYSTEM EVALUATION
Approval of
Region V's
Managing
Di rectors
*r
N
/
Direction of
Re-Evaluation,
if Required
Report of Compliance
Agency Procedures
for Evaluations of
Monitoring Programs
Region V s QA Program
for Implementation of
Agency Procedures for
Evaluation of Monitoring
Programs
Instructions
Evaluator
for
Execution of On-Site
Evaluation
Results of On-Site
Evaluation
Je
Report
Evaluation
Meeting for Discussion
of Report and
Recommendations
Corretive Action
for Compliance
>
Check of Results
after Compliance
Reports to
Management
JL
>
Monitoring Program
in Compliance with
Agency's Minimum
Quality Assurance
Requi rements
Di rections for
Special On-Site
Evaluations
-£j Immedi.
HReport and Review
->
Task Force
for Compliance
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APPENDIX 18
ELEMENTS FOR A SECTION 106, 208, 404(b)(l) AND GREAT LAKES _
NATIONAL PROGRAM MONITORING QUALITY ASSURANCE PROGRAM
1. The laboratory shall document and implement a Quality Assurance Policy
to assure sufficient quality control activities are maintained to assure
data credibility for each monitoring project. Management or supervisory |
quality control duties and responsibilities must be defined for its own
monitoring and for contract projects. «
2. A Quality Assurance Coordinator shall be designated by each laboratory
to coordinate quality control activities and to assure that they are
being performed. If quality control is not practiced, then there can I
be no quality assurance. I
3. Documented, technique oriented collection procedures shall be implemented
by each agency to assure valid and representative samples for surface I
waters, ground waters, point source discharges, fish, sediment, etc.
Uniform record keeping will be established to provide data credibility
and sufficient "chain-of-custody". I
4. Field measurement methodologies shall be used that are appropriate for
each monitoring project. Reference or approved methods must be used
for monitoring. Calibration and preventive maintenance protocols are |
to be established and used for all field instruments and methodologies.
Records of the calibrations and maintenance are to be maintained.
5. Sample preservation protocols shall be established by EPA for consistency
with the compositing time period used during monitoring, transport time
between field and laboratory, and dictates of required laboratory
methodologies, etc. |
6. A uniform source of sample containers shall be established. Sufficient _
quality control will be established to assure the appropriateness of I
containers used for each monitoring project. *
7. Sufficient number of field and laboratory personnel trained in quality
control practices shall be available for each monitoring project. |
8. The laboratory will establish sufficient record keeping and sample
handling practices for sample receipt and analyses, consistent with I
field record keeping practices, in order to maintain data credibility
and sufficient "chain-of-custody".
9. Protocols will be established for and records will be kept of instrument I
calibration and maintenance in an agency's laboratory. Appropriate
protocols will be established and used to assure the acceptance of
designated laboratory prepared materials (eg. - distilled water) and I
purchased materials (eg. - microbiology media).
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APPENDIX 18 (Continued)
10. Each laboratory will utilize and document methodologies, appropriate in
precision, sensitivity and accuracy, for each monitoring project.
Reference or approved methods must be used for monitoring and are
subject to review by the QAO.
11. Intra-laboratory audits of controls or "spiked" samples, replicate
analyses, and reagent blanks are to be utilized, recorded, and documented
by each laboratory to assure the acceptance of data for each monitoring
project. Summaries or quality control charts for these intra-laboratory
audits can be utilized to document analytical performance. The ability
of these intra-laboratory aidit data to represent actual data quality
is dependent on the specific audits performed and an understanding of
their utility by a data user.
12. Inter-laboratory audits of independently prepared reference smples or
U.S. EPA quality control samples, when available, are to be used at a
minimum frequency of quarterly and their results documented as part of
an agency's quality assurance program. Inter-laboratory audits or
reference samples assure analytical accuracy and maintenance of
calibration accuracy of a laboratory's day-to-day intra-laboratory
quality control program.
13. Each laboratory is requested to participate in U.S. EPA's performance
sample program, usually scheduled once per year for monitoring agencies.
Results should be documented as part of an agency's quality assurance
program and can replace one of the above inter-laboratory audits.
14. A quality assurance program should assure that only data meeting
acceptance criteria for the above elements are used for each monitoring
project. Data in computerized data management or storage systems must
be audited or verified as being the same as the actual field and
laboratory results.
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GLOSSARY
Analytical or reagent blank: a blank used as a baseline for the analytical
portion of a method. For example, a blank consisting of a sample
from a batch of absorbing solution used for normal samples, but
processed through the analytical system only, and used to adjust
or correct routine analytical results.
Audit: A systematic check to determine the quality of operation of some
function or activity. Audits may be of two basic types: (1) performance
audits in which quantitative data are independently obtained for
comparison with routinely obtained data, or (2) system audits of a
qualitative nature that consist of an on-site review of a laboratory's
quality assurance program and physical facilities for sampling,
calibration and measurement.
Bioassay: Using living organisms to measure the effect of a substance,
factor, or condition.
Biomonitoring: The use of living organisms to test water quality at a
discharge site or downstream.
Blank or sample blank: a sample of a carrying agent (gas, liquid, or solid)
that is normally used to selectively capture a material of interest
and that is subjected to the usual analytical or measurement process
to establish a zero baseline or background value, which is used to
adjust or correct routine analytical results.
Calculation: The arithmetic conversion of raw analytical data to some
standardized dimension form suitable for formating in a data report
or for its final intended use. For example, "x" ml/500 ml sample or
reagent might be calculated to be 10 mg/liter of zinc chloride which
exceeds the discharge limitations of a specific permit.
Calibration: Establishment of a relationship between various calibration
standards and the measurements of them by a measurement system (or
portions thereof). The levels of calibration standard should bracket
the range of levels for which actual measurements are to be made.
Completeness: The amount of valid data obtained from a measurement system
compared to the amount that was expected to be obtained under correct
normal operations.
Confidence interval: A value interval that has a designated probability
(the confidence coefficient) of including some defined parameter of
the population.
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Confidence limits: The outer boundaries of a confidence interval. I
Contract: The legal instrument reflecting a relationship between the
Federal Government and a State or local government or other recipient: J
(1) whenever the principal purpose of the instrument is the acquisition,
by purchase, lease, or barter, of property or services for the direct
benefit or use of the Federal Government; or (2) whenever an executive I
agency determines in a specific instance that the use of a type of
procurement contract
Cooperative agreement: The legal instrument reflecting the relationship |
between the Federal Government and a State or local government or
other recipient whenever: (1) the principal purpose of the relationship _
is the transfer of money, property, services, or anything of value I
to the State or local government or other recipient to accomplish
a public purpose of support or stimulation authorized by Federal
statute, rather than acquisition, by purchase, lease, or barter, of
property or services for the direct benefit or use of the Federal |
Government; and (2) substantial involvement is anticipated between
the executive agency acting for the Federal Govenrment and the State
or local government or other recipient during performance of the I
contemplated activity.
Data validation: A systematic effort to review data to identify any
outliers or errors and thereby cause deletion or flagging of suspect
values to assure the validity of the data to the user. This
"screening" process may be done by manual and/or computer methods,
and it may utilize any consistent technique such as sample limits to I
screen out impossible values or complicated acceptable relationships
of the data with other data.
In-house project: A project carried out by EPA staff in EPA facilities. I
Inter-laboratory: Between two different laboratories.
Intra-laboratory: Within a given laboratory.
Measures of dispersion or variability: Measures of the differences,
scatter, or variability of values of a set of numbers. Measures of
the dispersion or variability are the range, the standard deviation,
the variance, and the coefficient of variation.
Performance audit: Planned independent (duplicate) sample checks of
actual output made on a random basis to arrive at a quantitative _
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measure of the quality of the output. These independent checks are
made by an auditor subsequent to the routine checks by a field
technician or laboratory analyst.
Performance test sample: A sample or sample concentrate (to be diluted
to a specified volume before analysis) of known (to the EPA only)
true value which has been statistically established by inter!aboratory
tests. These samples are commonly provided to laboratories to test
analytical performance. Analytical results are reported to the EPA
for evaluation.
Proficiency testing: Special series of planned tests to determine the
ability of field technicians or laboratory analysts who normally
perform routine analyses. The results may be used for comparison
against established criteria, or for relative comparisons among the
data from a group of technicians or analysts.
Program: The technical office or staff that has responsibility for a part
of the Agency's operation. For R&D grants, the "programs" are the
Office of Research and Development, the Office of Air Quality Planning
and Standards, the Office of Solid Waste Management Programs, and
the Office of Mobile Sources Air Pollution Control.
Project officer: The EPA official designated in the grant or contract
agreement as the Agency's principal contact with the grantee on a
particular grant. This person is the individual responsible for
project monitoring and for recommendations on or approval of proposed
project changes.
Quality: The totality of feature and characteristics of a product or
service that bears on its ability to satisfy a given purpose. For
pollution measurement systems, the product is pollution measurement
data, and the characteristics of major importance are accuracy.
precision, and completeness. For monitoring systesm, "completeness",
or the amount of valid measurements obtained relative to the amount
expected to have been obtained, is usually a very important measure
of quality. The relative importance of accuracy, precision, and
completeness depends upon particular purpose of the user.
Quality Assurance: (1) An organization's total program for assuring the
reliability of the data it produces.
(2) A system for integrating the quality planning,
quality assessment, and quality improvement efforts of various groups
in an organization to enable operations to meet user requirements
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at an economical level. In pollution measurement systems, quality I
assurance is concerned with all of the activities that have an
important effect on the quality of the pollution measurements, as well
as the establishment of methods and techniques to measure the quality |
of the pollution measurements. The more authoritative usages
differentiate between "quality assurance" and "quality control",
where quality control is "the system of activities to provide a
quality product" and quality assurance is "the system of activities H
to provide assurance that the quality control system is performing
adequately".
Quality assurance manual: An orderly assembly of management policies,
objectives, principles, and general procedures by which an agency
or laboratory outlines how it intends to produce quality data.
Quality assurance plan: An orderly assembly of detailed and specific
procedures by which an agency or laboratory delineates how is
produces quality data for a specific project or measurement method. I
A given agency or laboratory would have only one quality assurance
manual, but would have a quality assurance plan for each of its
projects or programs (group of projects using the same measurement I
methods; for example, a laboratory service group might develop a
plan by analytical instrument since the service is provided to a
number of projects). I
Quality control: The detailed and specific procedures used to insure the
quality of data produced by a particular measurement activity; the
system of activities designed and implemented to provide a quality I
product.
Quali ty control (internal): The routine activities and checks, such as I
periodic calibrations, duplicate analyses, use of spiked sample, etc.,
included in normal internal procedures to control the accuracy and
precision of a measurement process.
Quality control (external): The activities which are performed on an
occasional basis, usually initiated and performed by persons outside _
normal routine operations, such as on-site system surveys, independent I
performance audits, interlaboratory comparisons, etc., to assess
the capability and performance of a measurement process.
Range: The difference between the maximum and minimum values of a set |
of values. When the number of values is small (i.e., 12 or less), the
range is a relatively sensitive (efficient) measure of variability. _
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Reagent: A chemical material, usually a compound of high purity, which is
used as a reactant in the process of a chemical analysis.
Recovery: That percentage of a parameter in a sample which is detected
or "recovered" from that sample during chemical analysis.
Reliability: A numerical statement of accuracy and precision.
Representativeness: A numerical statement of how well a sample or group
of samples or the data derived therefrom represents the actual
parameter variations at the sampling point, plus how well that
sampling point represents the actual parameter variations which
are under study.
Sample: A subset or group of objects or things selected from a larger
set called the "lot" or "population". The objects or things may
be physical, such as specimens for testing, or they may be data
values representing physical samples. Unless otherwise specified,
all samples are assumed to be randomly selected. Samples can take
numerous forms, such as:
Representative sample: A sample taken to represent a lot or population
as accurately and precisely as possible. A representative sample may
be either a completely random sample or a stratified sample, depending
upon the objective of the sampling and the conceptual population for
a given situation.
Spiked sample: A normal sample of material (gas, solid, or liquid)
to which is added a known amount of some substance of interest. The
extent of the spiking is unknown to those analyzing the sample. Spiked
samples are used to check on the performance of a routine analysis or
the recovery efficiency of a method.
Standard deviation: The square root of the variance of a set of values:
n 9
(X1 - X)2
s = i = 1
n - 1
if the values represent a sample from a larter population:
N
(Xi - u)2
i = 1
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Calibration standard: A standard prepared by the analyst for the
purpose of calibrating an instrument. Laboratory control standards
are prepared independently from calibration standards for most methods.
Detection limit: That number obtained by adding two standard deviations
to the average value obtained for a series of reagent blanks that are
analysed over a long time period (several weeks or months).
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where u is the true arithmetic mean of the population. The property |
of the standard deviation that makes it most particularly meaningful
is that it is in the same units as the values of the set, and
universal statistical tables for the normal (and other) distributions I
are expressed as a function of the standard deviation. Mathematically,
the tables could just as easily be expressed as a function of the
variance. I
Standard reference material (SRM): A material produced in quantity, of
which certain properties have been certified by the National Bureau
of Standards (NBS) or other agencies to the extent possible to satisfy J
its intended use. The material should be in a matrix similar to
actual samples to be measured by a measurement system or be used
directly in preparing such a matrix. Intended uses include: I
(1) standardization of solutions, (2) calibration of equipment, and
(3) monitoring the accuracy and precision of measurement systems.
Standard reference sample: A carefully prepared material produced from or |
compared aganist an SRM (or other equally well characterized material)
such that there is little loss of accuracy. The sample should have a _
matrix similar to actual samples used in the measurement system. These I
samples are intended for use primarily as reference standards to: *
(1) determine the precision and accuracy of measurement systems,
(2) evaluate calibration standards, and (3) evaluate quality control
reference samples. They may be used "as is" or as a component of a |
calibration or quality control measurement system. Examples: an
NMS-certified sulfur dioxide permeation device is an SRM. When used
in conjunction with an air dilution device, the resulting gas becomes I
an SRS. An NBS-certified oxide gas is an SRM. When diluted with air,
the resulting gas is an SRS.
Standardization: A physical or mathematical adjustment or correction of a I
measurement system to make the measurements conform to predetermined
values. The adjustments or corrections are usually based on a
single-point calibration level. I
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7
Duplication analyses: The collection of two samples from the same
field-site which are analyzed at different times but usually on the
same day.
Laboratory control standard: A standard of known concentration
prepared by the analyst.
Reference standard: A solution obtained from an outside source
having a known value and analyzed as a blind sample.
Relative percent error for duplicate analyses: The difference between
the measured concentration for the duplicate pair times 100 and
divided by the average of the concentration.
Relative percent error for laboratory control standards: The difference
between the measured value and the theoretically correct value times
100 and divided by the correct value.
Relative percent error of a reference sample analysis: The difference
between the correct and measured values times 100 and divided by the
correct concentration.
Standards based upon usuage:
Calibration standard: A standard used to quantitate the relationship
between the output of a sensor and a property to be measured.
Calibration standards should be traceable to standard reference
materials or primary standard.
Quality control reference sample (or working standard): A material
used to assess the performance of a measurement or portions thereof.
It is intended primarily for routine intralaboratory use in maintaining
control of accuracy and would be prepared from or traceable to a
calibration standard.
Standards depending upon "purity" or established physical or chemical constants:
Primary standard: A material having a known property that is stable,
that can be accurately measured or derived from established physical
or chemical constants, and that is readily reproducible.
Secondary standard: A material having a property that is calibrated
against a primary standard.
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Standards in naturally-occurring matrix: Standards relating to the pollutant
measurement portions of air pollution measurement systems may be
categorized according to matrix, purity, or use. Standards in a |
naturally-occurring matrix include Standard Reference Materials and
Standard Reference Samples.
Statistical control chart (also Shewhart control chart): A graphical chart
with statistical control limits and plotted values (usually in
chronological order) of some measured parameter for a series of
samples. Use of the charts provides a visual display of the pattern |
of the data, enabling the early detection of time trends and shifts
in level. For maximum usefulness in control, such charts should be m
plotted in a timely manner, i.e., as soon as the data are available. I
System audit: A systematic on-site qualitative review of facilities,
equipment, training, procedures, record-keeping, validation, and
reporting aspects of total (quality assurance) system to arrive at I
a measure of the capability and ability of the system. Even though
each element of the system audit is qualitative in nature, the
evaluation of each element and the total may be quantified and I
scored on some subjective basis.
Systematic error: The condition of a consistent deviation of the results I
of a measurement process from the reference or known level.
Test Variability: Accuracy: The degree of agreement of a measurement (or
an average of measurements of the same thing), X, with an accepted |
reference or true value, T, usually expressed as the difference
between the two values, X-T, or the difference as a percentage of the
reference or true value, 100(X-T)/T, and sometimes expressed as a I
ratio, X/T.
Bias: A systematic (consistent) error in test results. Bias can
exist between test results and the true value (absolute bias, or lack |
of accuracy), or between results from different sources (relative
bias). For example, if different laboratories analyze a homogeneous
and stable blind sample, the relative biases among the laboratories I
would be measured by the differences existing among the results from *
the different laboratories. However, if the true value of the blind
sample were known, the absolute bias or lack of accuracy from the I
true value would be known for each laboratory. I
Precision: A measure of mutual agreement among individual measurements
of the same property, usually under prescribed similar conditions. I
Precision is most desirably expressed in terms of the standard
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deviation but can be expressed in terms of the variance, range, or
other statistics. Various measures of precision exist depending upon
the "prescribed similar conditions".
Replicates: Repeated but independent determinations of the same
sample, by the same analyst, at essentially the same time and same
conditions. Care should be exercised in considering replicates of a
portion of an analysis and replicates of a complete analysis. For
example, duplicate titrations of the same digestion are not valid
replicate analyses, although they may be valid replicate titrations.
Replicates may be performed to any degree, e.g., duplicates, triplicates,
etc.
Rejproducibility: The precision, usually expressed as a standard
deviation, measuring the variability among results of measurements
of the same sample at different laboratories.
Validation: A systematic effort to review data to identify outliers or
errors and thereby cause deletion or flagging of suspect values to
assure the validity of the user's data.
Variance: Mathematically, for a sample, the sum of squares of the
differences between the individual values of a set and the arithmetic
mean of the set, divided by one less than the number of values.
Verification: Follows validation and permits the certification of the data
for an intended legal use, presuming that the chain-of-custody require-
ments are found to be intact. Again the terminology used in this
document is intended to be general and should in no way be construed
to limit the use of special area terminologies in the preparation
of the required QA Plan.
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TECHNICAL REPORT DATA
(Please read Instructions on the reverse ve/ore completing)
1. REPORT NO.
EPA-905/4-80-001
3. RECIPIENT'S ACCESSION-NO.
4. TITLE AND SUBTITLE
Quality Assurance Program, Guidelines and
Specifications, Criteria and Procedures,
Region V
5. REPORT DATE
January 15, 1980
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
James H. Adams, Jr.
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Quality Assurance Office
Surveillance and Analysis Division
U.S. Environmental Protection Agency
Chicago, Illinois 60605
10. PROGRAM ELEMENT NO.
Region V
11. CONTRACT/GRANT NO.
12. SPONSORING AGENCY NAME AND ADDRESS
Quality Assurance Office
Surveillance and Analysis Division
U.S. Environmental Protection Agency
Chicago, Illinois 60605
13. TYPE OF REPORT AND PERIOD COVERED
Manual
Region V
14. SPONSORING AGENCY CODE
15.SUPPLEMENTALY^NOTES Manuai wi 11 be reproduced in the current format (plastic Dinding)
maintained up-to-date by the QAO, Region V. Distribution will be to Agency personnel
and its contractors, State and local agency laboratory Directors and QC offices in
Rag-i-nit V
i\cy i VJM r;
16. ABSTRACT
This manual documents the Quality Assurance Program for Region V, U.S. EPA, that will
produce a numerical estimate'of the reliability of all data values reported or used
by the Region. Revisions will be made per the requirements of the finalized Quality
Assurance Plan of the--Agency. The elements of a quality assurance program are
discussed, including Region V's QA Policy Statement, Objectives and Milestones,
Quality Assurance-Management, Personnel, .Facilities, Equipment and Services, Review
of Program Plans, Project Plans'or Study Plans, Data Collection, Data Processing,
Corrective Actions, Data Quality Assessment, Data Quality Reports, Chain of Custody
and Specific Guidance.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.IDENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Quality Assurance
Quality Control
Intralaboratory QC
Inter!aboratory QC
Performance and 'System
Audits
Quality Control Program
Accuracy Assessment
Precision Assessment
13B
14B
18. DISTRIBUTION STATEMENT
Release Unlimited
19. SECURITY CLASS (This Report)
Unclassified
21. NO. OF PAGES
237
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (3.73)
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INSTRUCTIONS
1. REPORT NUMBER
Insert the EPA report number as it appears on the cover of the publication.
2. LEAVE BLANK
3. RECIPIENTS ACCESSION NUMBER
Reserved for use by each report recipient.
4. TITLE AND SUBTITLE
Title should indicate clearly and briefly the subject coverage of the report, and be displayed prominently. Set subtitle, if used, in smaller
type or otherwise subordinate it to mam title. When a report is prepared in more than one volume, repeat the primary title, add volume
number and include subtitle for the specific title. ,
5. REPORT DATE
Each report shall carry a date indicating at least month and year. Indicate the basis on which it was selected (e.g., date of issue, date of
approval, date of preparation, etc.),
6. PERFORMING ORGANIZATION CODE
Leave blank.
7. AUTHOR(S)
Give name(s) in conventional order (John R. Doe, J. Robert Doe, etc.). List author's affiliation if it differs from the performing organi-
zation.
8. PERFORMING ORGANIZATION REPORT NUMBER
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9. PERFORMING ORGANIZATION NAME AND ADDRESS
Give name, street, city, state, and ZIP code. List no more than two levels of an organizational hiiearchy
10. PROGRAM ELEMENT NUMBER
Use the program element number under which the report was prepared. Subordinate numbers may be included in parentheses.
11. CONTRACT/GRANT NUMBER
Insert contract or grant number under which report was prepared.
12, SPONSORING AGENCY NAME AND ADDRESS
Include ZIP code.
13. TYPE OF REPORT AND PERIOD COVERED
Indicate interim final, etc., and if applicable, dates covered. - *
14. SPONSORING AGENCY CODE
Leave blank.
15. SUPPLEMENTARY NOTES " " . - - - - '
Enter information not included elsewhere but useful, such as: Prepared in cooperation with. Translation of. Presented at conference of,
To be published in, Supersedes. Supplements, etc.
16. ABSTRACT
Include a brief (200 words or less) factual summary of the most significant information contained in the report. If the report contains a
significant bibliography or literature survey, mention it here.
17. KEY WORDS AND DOCUMENT ANALYSIS
(a) DESCRIPTORS - Select from the Thesaurus of Engineering and Scientific Terms the proper authorized terms that identify the major
concept of the research and are sulficiently specific and precise to be used as index entries for cataloging.
the primary posting(s).
18. DISTRIBUTION STATEMENT
Denote releasability to the public or limitation for reasons other than security for example "Release Unlimited." Cite any availability to
the public, with address and price. ,
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22. PRICE
Insert the price set by the National Technical Information Service or the Government Printing Office, if known.
1
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(b) IDENTIFIERS AND OPEN-ENDED TERMS - Use identifiers for project names, code names, equipment destenators, etc. Use open- I
ended terms written in descriptor form for those subjects for which no descriptor exists.
(c) COSATI FIELD GROUP - Field and group assignments are to be taken from the 1965 COSATI Subject Category List. Since the ma-
jority of documents are muitidisciclinary in nature, the Primary Field/Group assignment!*) will be specific discipline, irea of human a
endeavor, or type of physical object. The appucation(s) will be cross-referenced with secondary Field, Group assignments that will follow
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S U.S. Environmental Protection
Great Lakes Kntloral Program Offtee
---- GLNTO Library '
EPA Form 2220-1 (9-73) (Reverse) |
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